L4. Acids. Bases.

pH

Water ionization
Water is an amphoteric substance, functioning both as a proton donor (acid) and an
acceptor (base). Its dissociation produces hydronium (H3O+) and hydroxyl ions (HO-):
2H2O H3O+ + HO-
To simplify, we will refer for the hydronium ion as being hydrogen ion (H +) and we can write
the equilibrium as follows:
-
H2O H ++ HO
The equilibrium constant, Ke, of this reaction will be:
[ H + ] [ HO− ]
K e=
[ H2O] (1)
where the terms in brackets represent the molar concentrations. In pure water, the
concentration [H2O] is practically constant at 55 mol/L. Substituting this value into the
equation, it gives:
PH2O = KH2O = [H+] [HO-] (2)
where KH2O (PH2O) is the ionic product of water. At 25°C, KH2Ois1 · 10-14.

The H+ and HO- concentrations are reciprocally correlated. If the H+ concentration is

high, then the HO- concentration is low and vice—versa.

Acid and base definition

An acid in an ionolytic solvent (that dissociate in ions) is any dissolved substance,
more or less dissociated in ions and whose positive ions is identical with the one that results
from the solvent dissociation. In water, all the substances that dissociate hydrogen ions
(hydronium) will be acids. In liquid ammonia, where the ions: NH4+ and NH2- exist, all the
ammonium salts will be acids.
The ionization reaction of any acid can be represented as:
-
HA H ++ A
The equilibrium constant for this system is:
[ H + ][ A− ]
K a=
[ HA ] where Kais the acidity constant
As a function of this constant acids can be strong or weak. The strong acids are
totally ionized, and the weak ones are partially ionized.

A base in an ionolytic solvent is any dissolved substance, more or less dissociated in

ions and whose negative ion is identical with the one that results from the solvent
dissociation. In water, all the substances that dissociate hydroxyl ions will be bases.
A series of bases have ionic character even in the crystallized form, so they are totally
dissociated in solution. This is the category of the strong bases. There are other bases that
dissociate partially, as the following equilibrium:
-
BOH B++ HO
The equilibrium constant in this case is:

[ B+ ][ HO− ]
K b=
[ BOH ] where Kb is the basicity constant.
 For the strong bases Kb =1, and for the weak bases Kb< 1.
The product formed by the ionisation of an acid represents its conjugated base.
Reversely the protonation of a base gives rise to its to its conjugated acid.

pH definition
The pH is a measure of a solution’s concentration in hydrogen ions. It is calculated as
the negative decimal logarithm of the hydrogen ions concentration:
1
pH=log =−log [ H + ]
[H ]
+

Henderson - Hasselbalch equation – Dissociation constant

If the equation of the acidity constant is logarithmated, one will obtain:

[ +
] [ A− ]
log K e=log H + log
[ HA ]
[ A− ]
−log [ H + ]=−logK+log
[ HA ]
pH  pK  log
A 


 HA (Henderson-Hasselbalch equation)

The arrangement of the pH values from pH 0 ([H +] = 1) to pH 14 ([HO -] = 1) permits

to obtain a pH scale used in practice to give the hydrogen ion concentration of solutions.

pH calculation for acid, base and salt solutions

Strong acid and strong base solutions. These types of solutionsare considered to be
totally dissociated, so the hydrogen ions concentration will be equal with the equivalent
concentration of the acid or base. In this case:
[H+] = [HA] şi [HO–] = [BOH]
And so for the strong acid solutions:
pH = - log[HA]
and for strong base solutions:
pOH = - log[BOH] and pH = 14 – pOH

The neutralization reaction

The term neutralisation reaction usually is given to a reaction between a base and an
acid, with the formation of salt and water.

Volumetric analysis represents a group of analytic methods that are utilized for the
determination of the quantity of the analyzed component (ion, radical, element, complex
substance) by accurately measuring the volume of reagent solution (with a concentration
precisely known - the titrated solution), needed for the quantitative reaction. The equivalence
point corresponds to the stage of the titration at which the equivalent quantity (needed for a
100% reaction) of the titrated solution is added to the reagent to be determined. The quantity
of analyzed component is calculated from the reagent volume and the stoichiometry of the
known reaction. A burette is used to measure the exact volume of the reagent solution.
Titration represents the method by which volumes of a reagent solution (R1) are
added drop by drop to a known volume of another solution (R2) in order to determine its
concentration. The reaction is completed when the reagent regent R1 has reacted with the
whole quantity of reagent R2.
The reactions used in volumetric analysis must be complete and their finish to be easy
and accurately to determine. Consequently, it is necessary to know the equivalence point
exactly. In order to find out the equivalence point, the titration indicators are used.
Titration indicators are organic or inorganic substances that have the property to
change their color with the changing of medium conditions.
Some of the most frequently used indicators are:
- pH-indicators: methyl-orange, phenolphthalein;
- redox-indicators: methylene blue, 2,4-dichlorindophenol;
- complexonometric-indicators: calcon, murexide;
- precipitating-indicators: potassium chromate, diphenylcarbazone, etc

Indicators are used to establish the equivalence point (THEY DON’T PARTICIPATE TO
THE REACTION!!!).

The indication of the equivalence point in the volumetric analysis

Considering the titration operation – the titration reagent is added in small volumes to
an exact volume of the titrated substance until the analyzed substance has completely reacted
- we can say that, if the exact concentration of a reagent in known and also the moment in
which this reagent has been completely engaged in the reaction with the second reagent, we
can determine the concentration of the second reagent, knowing the chemical equation.
To indicate the end of the titration in the volumetric analysis, indicators are used. The
most used ones are colour indicators. Colour acid-base indicators are usually organic
compounds that modify their colour in a certain interval of pH (transition pH range).

pH Measurement
pH can be measured in different ways.

a) The potentiometric method

The most accurate method for pH measuring involves the use of a pH meter. The pH
meter is a potentiometer that measures the potential developed between a glass electrode and
a reference (calomel) electrode. A glass electrode consists of a silver wire coated with silver
chloride that dips into a reference solution of dilute hydrochloric acid. The hydrochloric acid
is separated from the test solution of unknown pH by a thin glass membrane. When a glass
electrode is immersed in the test solution, its electrical potential depends linearly on the
difference in the pH of the solutions on the two sides of the membrane.
In modern instruments, the two electrodes are frequently combined into one electrode,
known as a combination electrode.

Filling hole

Reference Electrod

Saturated KCl solution

KCl cristals Ceramic jonction

Electrod HCl 0,1 N solution

Ag0/AgCl

Glass membrane
 Combined glass electrode
The glass electrode contains a glass bulb, constructed of very thin special glass that is
permeable to hydrogen ions. As a result, a potential develops across this glass membrane.
Thus, the potential is linearly related to the pH. Standardization against a buffer of
known hydrogen ion concentration is required since the concentration of H+ inside the bulb of
the glass electrode changes with time.

b) The indicator method

Acid-base (pH) indicators are organic substances that change colour according to the
pH.
Examples of pH indicators

Indicator pKa Useful Colour

pH range Acidic Transition Basic
Form Form
Thymol blue 1.7 1.2 - 2.8 red orange yellow
Bromphenol blue 3.9 3.0 - 4.7 yellow green blue
Chlorophenol red 6.0 5.2 - 6.8 yellow orange red
Phenol red 7.8 6.6 - 8.0 yellow orange red
Phenolphthalein 9.5 8.3 - 10.0 colourless pink red

pH Indicator paper is a special filter paper, impregnated with different indicator.

These papers, when put in acid or base solution, change colour.

EXPERIMENTAL PART
ACID-BASE TITRATION
In an Erlenmeyer flask you will receive 10 mL of acetic acid/oxalic acid of unknown
concentration. To the acid solution, add 3-4 drops of phenolphtalein solution (pH indicator)
and homogenize well.
Titrate this solutions using NaOH 0.01M solution from the burette. Knowing the
volume of NaOH used to completely neutralize the acid solution (the solution in the
Erlenmeyer flask becomes pale pink!!), calculate the concentration of the acetic/oxalic acid
solution.