1. Concentrated vs. dilute acid and Strong vs.

weak acid

Concentrated acid remains in an unmixed configuration or has an elevated intensity.

Example: 98% w/w sulfuric acid is a highly intense acid.
When the density of the acid is less than the density of the water blended in it then it is a
dilute acid
Example: 5% w/w sulfuric acid in 95% water.
 A dilute acid can dissociate into ions to a higher level in their solution which is
dissimilar from concentrated acid (with decreasing concentration higher percentage of
dissociation).

 The pH of a concentrated acid mixed with water will be lower (higher acidity) than an
already aqueous diluted acid mixed with water, that is, pH will be high (lower
acidity). We can summarize this as higher the percentage of acid in water
(concentrated) the pH remains lower (more acidic). On the contrary, lower the
percentage of acid in water (diluted) the pH remains higher (less acidic).

 Dilute acids are 10 - 20% of the weight with 80 or 90% water. Concentrated acids are
96% of the weight with only 4-5% of water.

Example: Concentrated H2SO4 is made up 96% acid mixed with 4% water.

Concentrated HCl denotes 37% HCl (As HCl remains in gaseous form, therefore,
highest capacity that can be dissolved in H2Ois 37% w/w).

 In dilute acids, acid molecules are mixed with a large amount of water, meaning
concentration of H+ ions is low. In concentrated acids, acid molecules are mixed with
little to no water molecules meaning the concentration of H+ ions is high.
 Defining acid as per Bronsted-Lowry hypothesis, an acid is a material, it can be
molecule, cation or anion which can donate proton to other material. So, acid is a
donor of proton.

 Defining acid as per Lewis hypothesis, an acid is such a material (molecule/ anion/
cation) that can acquire a couple of electron. Therefore, Acid denotes as receiver of
electron couple.

 Definition

Strong Acid: The acids that totally ionize in aqueous medium to deliver maximum
possible amount of H+ are named strong acids. The strength of an acid can be
determined by the digits of the hydrogen ions (H+) formed by the ionization process
when the acid is in aqueous solution.

Example: HCl, HNO3, H2SO4 etc. are strong acids

HCl (aq) → H+ (aq) + Cl¯ (aq) [about 100% dissociates in 0.1 M HCl solution]

Weak acid: The acids that ionize in the aqueous solution partially to deliver lower
number of hydrogen ions in solution are named weak acids. The strength of an acid
can be ascertained by the digits of the H+ formed by the ionization process when the
acid is in aqueous solution.

Example: HCOOH (formic acid), CH3COOH (acetic acid) etc. organic acids are
weak acids. CH3COOH (aq) → H +(aq)+ CH3COO¯(aq) [about 5% dissociates in
0.1M solution]

 Strong acids totally ionize in aqua to yield the highest digits of H + ions. E.g.: 1 mol
H+ ions and 1 mol Cl– ions will be produced through the breakdown of 1 mol HCl. On
the contrary, weak acids don’t entirely dissociate in water. E.g.: Acetic acid
(CH3COOH), don’t totally ionize. H+ ions and CH3COO– ions are the resultants of the
breakdown of only one percent of acetic acid molecules.

 The pH values of weak acids are elevated than that of strong acids. Thus the reaction
ratio of strong acids with carbonate and hydrogen carbonate compounds of metal and
metal itself is elevated than that of weak acids.
 Temperature in strong acids is correspondingly elevated as the speedy reaction rate.
However, rate of reaction is slower in weak acids, thus rise in temperature is also
lower in them.
 2. Theory of color change of Indicator in titration
Indicator: To ascertain the equivalence or stopping place of the titration some particular
organic compounds are added to the solution in conical flask. At this end point there is visible
change of color. Such compounds are called indicators.
An indicator is a compound which shows idiosyncratic transition in its color when poured
(get in touch) in acid or base and that is why it is employed to ascertain in which level the
solution is acidic or basic. Litmus paper or its solution is good examples.
Contribution of indicators in analytical and titrimetric chemistry is salient. End point in a
titration is found out by their utilization. Weak acids or weak bases are organic compounds
abundantly utilized as indicators in acid-base titrations.
Amongst a definite pH range indicators transform their color which is shown below:
Indicator pH Range Color of Acidic Solution Color of Basic Solution
Methyl Orange 3.2-4.5 Orange Yellow
Methyl Red 4.4 – 6.5 Red Yellow
Bromothymol blue 6.0 -7.8 Yellow Blue
Phenolphthalein 8.3- 10.0 Colourless Pink
Alizarin Yellow 10.1 – 12.1 Yellow Red
Litmus 5.5-7.5 Red Blue
Phenol red 6.8-8.4 Yellow  Red
Two prominent Hypothesis that describe how indicators change colors with pH change.
I. Ostwald's Hypothesis

    As per Ostwald’s Hypothesis

 Indicators changes color because of ionization. The unionized and ionized forms of
indicators have no matching in color.
 An indicator can have weakly acidic property or weakly basic property, as a result
its ionization is extremely influencing in acids and bases. Let an indicator be a
weak acid, as a result by reason of common H+ ions, its ionization would be very
much low in acids while it is satisfactorily ionized in alkalis. Again, let the
indicator be a weak base, by reason of common OH - ions its dissociation into ions
is less in alkalis much in acids and Example: Weak acidic indicator
phenolphthalein and weak basic indicator methyl orange.
  Phenolphthalein

Phenolphthalein can be representated as HPh. As it is a weak acid, it ionizes in aqueous

media to a less degree as below:

HPh     H+ + Ph-

(Colourless) → Pink

Implementing mass action law, we get

 K = [H+][Ph-]/[HPh]
The unionized phenolphthalein molecules are colorless on the other hand the ionized
(Ph- ions) are pink colored. By reason of high concentration of H + ions in existence of an
acid, the equilibrium transports backwards or reverses (left side), dissociation of HPh into
ions is pragmatically trivial. In consequence, the solution will be colorless. If alkali is added,
OH- ions replace H+ in the form of H2O and the equilibrium transports forward (right side). In
consequence, Ph- ion density is elevated in the aqueous media and they appear to be pink
color in the aqueous media

Let us derive Handerson equation for an indicator

HIn    + H2O   H+3O  +   In-

'Acid form'               'Base form'

|                                        |

   Conjugate acid-base pair

Kln = [ln][H+3O]/[HIn];              KIn = Ionization constant for indicator

[H+3O] = KIn * [Hln]/ln-

pH = -log10 [H+3O] =  -log10[Kln] - log10[Hln]/[ln-]

pH = pKIn + log10[ln-]/[Hln]   (Handerson equation for indicator)

At equivalence point

[In-] = [HIn]  and  pH = pKIn

 Methyl Orange
Weakly basic methyl orange indicator is represented as MeOH. It dissociates into Me + and
OH- ions in aqueous media.
MeOH     Me+ + OH-

Yellow  → Red

Implementing mass action law,

 K = [Me+][OH- ]/[MeOH]
In existence of an acid, the above equilibrium transports forward (right side) as well as
OH- ions are withdrawn in the configuration of H 2O. In consequence, Me+ impart red
color and are adequately produced in the aqueous media. If alkali is added, the equilibrium
transports backward or reverses (left side) and the density of OH- ions intensifies in aqueous
media, that is, the dissociation into ions of MeOH is pragmatically trivial. In consequence,
the solution obtains the yellow colored unionized methyl orange compound.

This hypothesis also describes that phenolphthalein is not an appropriate indicator for
titrating a weakly basic compound in opposition to strongly acidic compound. A weak base
provides OH- ions which are not adequate to transport the equilibrium forward (right side)
substantially, that is, 8.3 in pH meter is not achieved. This is why the aqueous media do not
appear pink in color. Likewise, we can describe that methyl orange is not a compatible
indicator for titrating weakly acidic compound in oppositiob to strongly basic compound.
 II. Quinonoid Hypothesis
As per quinonoid hypothesis, indicators designed for acid – base remain in two tautomeric
configuration denoted as benzenoid and quinonoid which possess unlike structures and found
in equilibrium.

The two configurations have contrasting colors. Color transformation take place, in view of
interconversion of one tautomeric configuration to the other. One configuration remains in
medium that is acidic while other in basic. As a consequence, the aqueous medium
transforms its state from acidic to alkaline while titrating or vice-versa. The variation in pH
transforms one tautomeric configuration into another and because of that, the color
transformation take place.
In acidic solution Phenolphthalein remains in benzoic configuration and is colorless while in
alkaline solution it remains in quinonoid configuration and appears pink color.

In acidic solution Methyl orange remains in quinonoid configuration and is red colored,
while, in alkaline solution it remains in benzenoid configuration and appears yellow color

3. Limitation of aqueous titration in Penicillin Analysis

Limitation of water:
  As a titration medium the crucial disadvantage of water is its amphiprotic properties.
It will act as a competitive reagent because water itself is a weak acid or weak base.
H2O + H+ → H3O+
H2O + B → OH- + BH
Substances which are either too weakly basic (pKa<7) or too weakly acidic (pKa>7) cannot
be titrated accurately in aqueous medium. In this case, sharp end points cannot be detected.

 Some substances are decayed by water e.g. amide group containing drugs.
For this reason non-aqueous titration is necessary.
How to overcome:
Replacing the solvent (H2O) with other aprotic, protophilic or protogenic solvent.
Nonaqueous titration method: Titration of β lactam antibiotic can be done using
potentiometric method non-aqueous solvent other than water. In ethanol-benzene non
aqueous solvent fundamental compounds of penicillin got titrated either in counter with 0.1N
perchloric acid dissolved in acetic acid or with 0.1N p-toluene-sulfonic acid at a ratio of 1:9;
At the same time, in benzene-methanol non aqueous solvent 0.1N tetrabutylammonium
hydroxide got titrated with the acidic compounds. Back titrations are used if the
counterbalance is steady and/or acidic properties or basic properties are weaker. In anhydrous
benzene solvent back titration is conducted with phenol to ascertain the spare amount of
tetrabutylammonium hydroxide.
Structurally penicillins are medicinal chemicals with antibacterial property. Penicillin and its
derivatives conatin 6-aminopenicillanic acid (6-APA). They are compressed structures of 5
membered ring structure – thiazolidine, azetedine - A heterocycle ring structure containing
one nitrogen atom and three carbon atoms (β-lactam), and different functional group ‘R’
fused with the 6-APA. Major feature of them are bactericidal effect on the growth stage of
microorganisms with slight side effects on human organs.

The pKa value of Penicillin at room temperature (25° C) is 2.74 which is too weakly basic.
We know, substances which are either too weakly basic (pKa<7) cannot be titrated accurately
in aqueous medium. Thus non aqueous titration is required for Penicillin analysis and
aqueous titration will not provide accurate result or data for analysis.

4. Importance of Potentiometric titration in pH meter

Potential between reference electrode and indicator electrode is measured by a sort of
volumetric procedure designated as potentiometric titration.The potential difference in the
middle of reference and indicator electrodes is estimated as a function of density of the
reagents added to them.

Reference electrode have potential with (a) no dependency on the density of analyte ions in
liquid media; (b) no dependency on temperature.

Indicator electrode: It has potential and density of the analyte ions is the dependency of
indicator electrode potential. Example: Hydrogen ions

The endpoint of titration might be ascertained by combination electrodes or the couple of

electrodes. The endpoint dictates the specific point where the total specimen took part in
reaction. Significant span of potential transformation is accomplished at endpoint. The values
of Voltage and volume are recorded and plotted in a graph that gives a sigmoid curve. There
is a quick transformation in voltage vs volume slope when the stopping place/ endpoint is
obtained.

Figure: Voltage vs. volume slopes

Electrodes used to measure concentration:

Indicator electrodes and reference electrodes are used together to calculate potential of
unspecified liquid media.
E cell = E indicator – E reference + E j (Potential arising from salt bridge)
 Allocating alternatives depending on the requirement for ascertaining analytes a
number of categories of potentiometric titrations exist. Example: Acid-base titration,
complexometric titration, Redox potentiometric titration, Precipitation titration.
 Potentiometric titrations are well compatible with mechanical-automated-
computerized and electrical systems, with prominent extent sample processing.

 Potentiometric titrations are economical and uncomplicated while more contemporary

techniques might be employed to ascertain pH level. Example: High performance
liquid chromatography (HPLC) and capillary electrophoresis (CE). They have the
potential to function automatically and calculations, calibration, data entry, graphical
representations are done with computerized system using softwares. These attributes
guarantee the uninterrupted adequacy of potentiometric titrations.

 It is applied in case of difficult or unfeasible detection of the end point by usual visual
methods such as:

 If there is lack of indicator

 For exceedingly hued or mixture with turbidity

 For solutions which are aqueous or diluted 10¯3, 10¯6 M.

5. Role of EDTA in Complexometric titration
Complexometric Titration or chelatometry is a category of volumetric investigation to
ascertain the endpoint of the titration at when the complex composition with color is
employed and eventually forms complex or chelate. Titration is a common laboratory method
that dictates the undisclosed concentration of an analyte that has to be identified. Quantitative
chemical analysis uses this procedure.

Indicators

Calmagite and Eriochrome Black T (EBT) react with calcium and magnesium and yields
complex compounds and transforms the color to pink from blue. As the color changes from
pink to blue we can designate Calmagite and Eriochrome Black T (EBT) as indicators which
in complexometric titration helps to reach the endpoint.

Role of EDTA in Complexometric Titration

 EDTA consists of 2 amino groups (NH2) and 4 carboxyl groups (COOH), elaborated
like ethylenediaminetetraacetic acid which is a complexometric indicator and a Lewis
base.

 EDTA also denoted as hexadentate ligand by dint of its proficiency to signify six lone
pair of electrons for establishing covalent bonds.

 Occupancy of compacted metal ions will bring about a definite transformation in the
color which will form a less potent complex.

 Complexing agents characterized as free acids and sparingly soluble in water.

 Before using EDTA, EDTA is transformed into sodium salts so that they become
compatible in water and poured in volumetric solutions.

 As they have sparing solubility in water they are employed in titrating method.

 To ascertain the simple metal ions existing in water simple titration methods and to
ascertain the actual number of metal ions present complexometric titration is used
applying EDTA.
 To determine the hardness of water samples EDTA titrations are especially used.
Hardness is because of the existing Ca2+ and Mg2+ ions in water.

 The structure of a coloured complex for dictating the endpoint is utilized by

complexometric titration method. A common ligand EDTA, chemically denoted as
H4Y, is used in complexometric titrations.

 It contains 4 -COOH- and 2 -NH2- groups and contribute as donors of lone pair
electrons.

 Na2H2Y, disodium salt sometimes uses EDTA

 To compose a complex structure, metal ions readily undergoes reaction with EDTA
M2++H2Y2-⇌MY2-+2H+
The metal-EDTA complex structure is shown below:

If the reaction takes place in a basic buffer solution, H+ is readily removed whenever
it is formed.
 According to Le Châtelier's Principle this incidence transports the position of
equilibrium forward (right) and push forward to form the complex agent.
The pKa value of EDTA = 10.26.
As a result if the aqueous solution is buffered upto pH 10.3, nearly all of the EDTA will
remain as Y4- ions.
The metal ions will not be compelled to withdraw the H+ ions from H2Y2-.
They can react directly according to the equation
M2++Y4-→MY2-
Nearly all metal ions significantly take part in reaction with EDTA exceeding the pH
level 10.3.
6. Electric double layer of colloidal particle

In the electrostatic stabilization technique of colloidal particles, electric double layer is a

situation that contributes a rudimentary part. Let’s consider the colloidal particle in the figure
below. It received negative electrical charge around its surface by the adsorption of negative
electrically charged anions which was dissolved in the liquid dispersion medium. Now, the
negatively charged colloidal particle attracted the positive electrically charged cations in the
liquid dispersion media forming a layer.

Figure: an electric double layer is the layer surrounding a colloidal particle of dispersed phase

Explanation: In a liquid dispersion (solution) think about a colloidal particle. It carries either
positive or negative charge. Let the top surface of the colloidal particle be positively charged.
This positively charged colloidal particle is surrounded by negatively charged particles
present in the liquid dispersion (solution). This negatively charged particles form a layer
around the positively charged colloidal particle. The positively charged top surface of the
colloidal particle is a fixed layer; whereas the negatively charged layer is continuously
replaced, it comes from the liquid dispersion (solution), it is known as Diffused layer and it is
not fixed. These 2 layers are together known as electrical double layer.

These 2 layers are separated by very small distance. When there are two opposite charges,
there is potential difference between the positively charged colloidal particle and negatively
charged layer surrounding the colloidal particle. This potential difference between 2 layers is
known as Zeta potential or Electrokinetic potential.
 References:

 https://sciencing.com/purpose-titration-5406434.html (4)

 https://byjus.com/chemistry/complexometric-titration/ (5)

 https://socratic.org/questions/why-is--solution-used-in-complexometric-
titration (5)

 https://www.sciencedirect.com/topics/chemistry/electric-double-
layer#:~:text=An%20electric%20double%20layer%20is,adsorbed%20on
%20the%20particle%20surface. (6)

 https://www.jocpr.com/articles/quantitative-determination-of-some-
penicillin-by-iodometric-method-using-potassium-
peroxomonosulphate.pdf (3)

 https://www.askiitians.com/iit-jee-chemistry/physical-chemistry/theory-of-
indications.aspx (2)

 https://socratic.org/questions/5746df8b11ef6b773de66e2e (1)

 https://www.bbc.co.uk/bitesize/guides/zrx3rwx/revision/3 (1)

 https://chemistry.stackexchange.com/questions/28001/is-there-a-
difference-in-the-reactions-of-a-dilute-acid-and-a-concentrated-acid (1)

 https://www.chemguide.co.uk/physical/acidbaseeqia/acids.html (1)