ACKNOWLEDGEMENT

We would like to express our special thanks of gratitude to our chemistry teachers Mr.Melwin.G.Antony and
Mr.Sagnik Bhattacharya as well as our principal, Mrs. Jyothis ma’am for providing us with the opportunity
to work on this beautiful project. Secondly, we would also like to thank our parents and friends who helped
us finish this project within the limited time frame. Finally, we would like to thank everyone without whose
help we could not have completed our project successfully.
 INDEX

1. Cover Page
2. Certificate page
3. Acknowledgement
4. Index
5. Aim/Title
6. Objectives
7. Apparatus
8. Introduction
9. Theory
10. Method
11. Result
12. Analysis and Interpretation
13. Conclusion
14. Bibliography
 AIM / TITLE
Study of the pH scale from an Ionic Equilibrium standpoint

OBJECTIVES
To study the change in pH and calculate it.

APPARATUS

INTRODUCTION
pH is a unit of measure which describes the degree of acidity or alkalinity of a solution. It is measured on a
scale of 0 to 14. The term pH is derived from “p,” the mathematical symbol for negative logarithm, and “H,”
the chemical symbol for Hydrogen. The formal definition of pH is; the negative logarithm of Hydrogen ion
activity.
pH = -log[H+]
pH provides needed quantitative information by expressing the degree of activity of an acid or base in terms
of its hydrogen ion activity.
The pH value of a substance is related to the ratio of hydrogen ion [H+] and hydroxyl ion [OH-]
concentrations. If the H+ concentration is greater than the OH-, the material is acidic; that is, the pH value is
less than 7. If the OH concentration is greater than its H+, the material is basic, with a pH value greater than
7. If equal numbers of H+ and OH ions are present, the material is neutral, with a pH of 7.
Acids and bases have free hydrogen and hydroxyl ions, respectively. Since the relationship between
hydrogen ions and hydroxyl ions in a given solution is constant for a given set of conditions, either one can
be determined by knowing the other. Thus, pH is a measurement of both acidity and alkalinity, even though
by definition it is a selective measurement of hydrogen ion activity.

THEORY
pH and pOH
• In chemistry, pH, also referred to as acidity or basicity, historically denotes ‘potential of hydrogen’ or
‘power of hydrogen’.
• It is a scale use to specify the acidity or basicity of an aqueous solution.
• Acidic solutions (solutions with higher concentrations of hydrogen ions) are measured to have lower
pH values than basic or alkaline solutions.
• The pH scale is logarithmic and inversely indicates the activity of hydrogen ions in the solution

Where [H+] is the equilibrium molar concentration (mol/L) of [H+] in the solution. At 25 °C,
solutions with a pH less than 7 are acidic, and solutions with a pH greater than 7 are basic, and
solutions with a pH greater than 7 are basic.
• Solutions with a pH of 7 at 25 °C are neutral. The neutral value of the pH depends on the temperature
and is lower than 7 if the temperature increases above 25 °C.
• The pH value can be less than 0 for very concentrated strong acids or greater than 14 for very
concentrated strong bases.
• The pH scale is traceable to a set of standard solutions whose pH is established by international
agreement. Primary pH standard values are determined using a concentration cell with transference
by measuring the potential difference between a hydrogen electrode and a standard electrode such as
the silver chloride electrode.
• The pH of aqueous solutions can be measured with a glass electrode and a pH meter or a colour-
changing indicator. Measurements of pH are important in chemistry, agronomy, medicine, water
treatment, and many other applications.

History
• In 1909, the Danish chemist Soren Peter Lauritz Sorensen introduced the concept of pH at the
Carlsberg Laboratory, originally using the notation “pH•", with H• as a subscript to the lowercase p.
• The concept was later revised in 1924 to the modern pH to accommodate definitions and
measurements in terms of electrochemical cells.

‘’For the sign p, I propose the name 'hydrogen ion exponent' and the symbol pH•. Then, for the
hydrogen ion exponent (pH•) of a solution, the negative value of the Briggsian logarithm of the
related hydrogen ion normality factor is to be understood’’
• Sorensen did not explain why he used the letter p, and the exact meaning of the letter is still disputed.
• Sorensen described a way of measuring pH using potential differences, and it represents the negative
power of 10 in the concentration of hydrogen ions.
• The letter p can stand for the French puissance, German Potenz, or Danish potens, all meaning
power, or it could mean ‘’potential’’. All of these words start with the letter p in French, German or
Danish, which were the languages in which Sorensen published: Carlsberg Laboratory was French
speaking; German was the dominant language of scientific publishing; Sorensen was Danish.
• He also used the letter q in much the same way elsewhere in the paper, and he might have arbitrarily
labelled the test solution ‘’p’’ and the reference solution ‘’q’’; these letters are often paired.
• Some literature sources suggest that ‘’pH’’ stands for the Latin term pondus hydrogenii or potential
hydrogenii, although this is not supported by Sorensen’s writings.

Definition
pH
• The pH of a solution is defined as the decimal logarithm of the reciprocal of the hydrogen ion
activity aH+. Mathematically pH is expressed as

• For example, for a solution with a hydrogen ion activity of 5×10−6 (i.e., the concentration of
hydrogen ions in moles per litre), the pH of the solution can be calculated as follows:

• The concept of pH was developed because ion-selective electrodes, which are used to measure,
respond to activity. The electrode potential, E, follows the Nernest equation for the hydrogen ion,
which can be expressed as

Where E is a measured potential, E0 is the standard electrode potential, R is the gas constant, T is the
temperature in Kelvin, F is the Faraday constant. For H+, the number of electrons transferred is one.
The electrode potential is proportional to pH when pH is defined in terms of activity.
• The precise measurement of pH is presented in International Standard ISO 31-8 as follows: A
galvanic cell is set up to measure the electromotive force between a reference electrode and an
electrode sensitive to the hydrogen ion activity when they are both immersed in the same aqueous
solution. The reference electrode can be a silver chloride electrode or a calomel electrode, and the
hydrogen ion selective electrode is a standard hydrogen electrode.

Firstly, the cell is filled with a solution of known hydrogen ion activity and the electromotive force,
ES, is measured. Then the electromotive force, EX, of the same cell containing the solution of the
unknown pH is measured.

• The difference between the two measured electromotive force values is proportional to pH. This
method of calibration avoids the need to know the standard electrode potential. The proportionality
constant, 1/z, is ideally equal to

, the ‘Nernstian slope’.

• In practice, a glass electrode is used instead if the cumbersome hydrogen electrode. A combined glass
electrode has an in-built reference electrode. It is calibrated against buffer solutions of known
hydrogen ion activity proposed by the International Union of Pure and Applied Chemistry.
• Two or more buffer solutions are used in order to accommodate the fact that the ‘slope’ may differ
slightly from the ideal. To calibrate the electrode, it is first immersed in a standard solution, and the
reading on a pH meter is adjusted to be equal to the standard buffer’s value.
 • The reading from a second standard buffer solution is then adjusted using the ‘slope’ control to be
equal to the pH for that solution.
• When more than two buffer solutions are used the electrode is calibrated by fitting observed pH
values to a straight line with respect to standard buffer values.
• Commercial standard buffer solutions usually come with information on the value at 25 °C and a
correction factor applied for other temperatures.
• The pH scale is logarithmic and therefore pH is a dimensionless quantity.

Definition by Sorensen
• This was the original definition of Sørensen in 1909, [18] which was superseded in favour of pH in
1924. [H] Is the concentration of hydrogen ions, denoted [H+] in modern chemistry. More correctly,
the thermodynamic activity of H+ in dilute solution should be replaced by [H+]/c0, where the
standard state concentration c0 = 1 mol/L. This ratio is a pure number whose logarithm can be
defined.
• It is possible to measure the concentration of hydrogen ions directly using and electrode calibrated in
terms of hydrogen ion concentration. One common is to titrate a solution of known concentration of
a strong acid with a solution of known concentration of strong base in the presence of a relatively
high concentration of background electrolyte.
• By knowing the concentrations of the acid and base, the concentration of hydrogen ions can be
calculated and the measured potential can be correlated with concentrations. The calibration is
usually carried out using a Gran plot. This procedure makes the activity of hydrogen ions equal to the
numerical value of concentration.
• The glass electrode should be calibrated in a medium similar to the one being investigated. For
instance, if one wishes to measure the pH of a seawater sample, the electrode should be calibrated in
a solution resembling seawater in its chemical composition.

The difference between p [H] and pH is quite small, and it has been stated that pH = p [H] + 0.04. [20]
However, it is common practice to use the term "pH" for both types of measurement.

pOH
pOH is sometimes used as a measure of the concentration of hydroxide ions, OH−. pOH values are derived
from pH measurements. The concentration of hydroxide ions in water is related to the concentration of
hydrogen ions by

Where KW is the self-ionization constant of water. Taking logarithms

So, at room temperature, pOH ≈ 14 – pH. However, this relationship is not strictly valid in other
circumstances, such as in measurements of soil alkalinity.

Measurement
pH indicators
• pH can be measured using indicators, which change colour depending on the pH of the solution they
are in.
• By comparing the colour of a test solution to a standard colour chart, the pH can be estimated to the
nearest whole number. For more precise measurements, the colour can be measured using a
colorimeter or spectrophotometer. Universal indicator is a mixture of several indicators that can
provide a continuous colour change over a range of pH values, typically from about pH 2 to pH 10.
• Universal indicator paper is made from absorbent paper that has been impregnated with universal
indicator.
• An alternative method of measuring pH is using an electronic pH meter, which directly measures the
voltage difference between a pH sensitive electrode and a reference electrode.

Non aqueous solutions

• pH values can be measured in non – aqueous solutions, but they are based on a different scale from
aqueous pH values, because the standard states used for calculating hydrogen ion concentrations are
different. The hydrogen ion activity, aH+ , is defined as where μH+ is the chemical potential of the
hydrogen ion, is its chemical potential in the chosen standard state, R is the gas constant and T is the
thermodynamic temperature.

• Therefore, pH values on the different scales cannot be compared directly because of differences in
the solvated proton ions, such as lyonium ions, which require an intersolvent scale which involves
the transfer activity coefficient of hydronium/lyonium ion.
• pH is an example of an acidity function, but there are others that can be defined. For example, the
Hammett acidity function, H0, has been developed in connection with super acids.

Unified absolute pH scale

• In 2010, a new approach to measuring pH was proposed, called the ‘’unified absolute pH scale’’.
• This approach allows for a common reference standard to be used across different solutions,
regardless of their pH range.
• The unified absolute pH scale is based on the absolute chemical potential of the proton, as defined by
the Lewis acid-base theory. This scale is applicable to liquids, gases and even solids.
• The advantages of the unified absolute pH scale include consistency, accuracy, and applicability to a
wide range of sample types.
• It is precise and versatile because it serves as a common reference standard for pH measurements.
• However, implementation efforts, compatibility with existing data, complexity, and potential costs
are some challenges.

Extremes of pH measurements
• The measurement of pH can become difficult at extremely acidic or alkaline conditions, such as
below pH 2.5 or above pH 10.5
• This is due to the breakdown of the Nernst equation in these conditions when using a glass electrode.
• There are several problems contributing to this factor. Firstly, liquid junction potentials may not be
independent of pH.
• Secondly, the high ionic strength of concentrated solutions can affect the electrode potentials. At high
pH the glass electrode may be affected by ‘’alkaline error’’, because the electrode becomes sensitive
to the concentration of cations such as Na+ and K+ in the solution.
 • To overcome these problems, specially constructed electrodes are available.
• Runoff from mines or mine tailings can produce some extremely low pH values.

METHOD
1. We take various samples of liquids, as of this experiment it is the following :
Water, Vanilla essence, Soy sauce, Lemon, Vinegar, Baking Powder, Hand wash, Detergent
[The order of the pH papers in the above picture are from left (water) to right (detergent)]
2. Now we take pH papers and put one drop of one liquid per paper.
3. We wait for a minute for the effect to start and after that we see a change in the colour of the papers,
and we match it with the pH scale.
4. We can use the formulas to calculate the ionic product and match it to the pH scale.

RESULT
Relation between pH and Equilibrium:
We are surrounded by dilute solutions of acids and bases, inside and out. The orange juice and coffee that
help us start our day are acidic, and the gastric juices they mix with in our stomach are also naturally acidic.
Many of our household cleaning liquids, like the detergent solution in our washing machines and the bleach
we add to whiten our clothes, are basic. Now that the reversible reactions are known and how solutions are
described in terms of molarity, let us understand the origin of the pH scale for describing acids and what the
pH value says about an acidic or basic solution.
Pure water undergoes a reversible reaction in which both H+ and OH- are generated.

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

The equilibrium constant for this reaction, called the water dissociation constant, Kw, is 1.01 × 10-14 at 25
°C.
Kw = [H+][OH-] = 1.01 × 10-14 at 25 °C
Because every H+ (H3O+) ion that forms is accompanied by the formation of an OH- ion, the
concentrations of these ions in pure water are the same and can be calculated from Kw.
Kw = [H+][OH-] = (x)(x) = 1.01 × 10-14
x = [H+] = [OH-] = 1.01 × 10-7 M
(1.005 × 10-7 M before rounding)

we have a few formulas given;

pH = -Log[H3O-]
pH = -Log[H+]
pOH = -Log[OH-]
pKw = pH + pOH (here pKw is the dissociation constant of water)
14 = pH + pOH

Let’s understand why (pH + pOH = 14)?

Water, whether it's on its own or part of an aqueous solution, undergoes self-ionization which can be
represented by the equation:
2 H2O ⇆ H3O+ + OH-
Equilibrium forms between the unionized water and the hydronium (H3O+) and hydroxide (OH-) ions.

The expression for the equilibrium constant Kw is:

Kw = [H3O+][OH-]
Strictly speaking, this relationship is only valid for aqueous solutions at 25°C because that is when the value
of Kw is 1 x 10-14.
If you take the log of both side of the equation:
log (1 x 10-14) = log [H3O+] + log [OH-]
(When numbers are multiplied, their logs are added.)

log (1 x 10-14) = - 14
- 14 = log[H3O+] + log [OH-]
Multiplying both sides of the equation by -1:
14 = - log [H3O+] - log [OH-]
pH is defined as - log [H3O+] and pOH is defined as -log [OH-], so the relation becomes:
14 = pH - (-pOH)

14 = pH + pOH

* When a Weak Acid & a Weak Base is combined;

pH = 7 + ½ (pKa – pKb)
* When a Weak Acid & a Strong base is combined;
pH = ½ pKw + ½ pKa + ½ logC
* When a Strong Acid & a Weak Base is combined;
pH = ½ pKw – ½ pKb – ½ logC

ANALYSIS AND INTERPRETATION

The formula was used to find the values and we can infer that pH can be found not only using the papers but
also using the formulas.
 CONCLUSION
The conclusion from the pH experiment can give us an idea of how the pH scale was created and what are
the basis regarding it. We can also find out the ionic product and using the concepts of equilibrium we attain
our results which match the pH scale.

BIBLIOGRAPHY
Google
Wikipedia
NCERT source textbooks
Allen modules