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REFRESHER COURSE IN CHEMISTRY

FOR HIGHER EDUCATION FACULTY
(2018)

Module 10: ChemMisconception: pH

(Month of Publication: September, 2018)

Developed at

NATIONAL RESOURCE CENTRE OF CHEMISTRY

MHRD, Govt. of India

at
Guru Angad Dev Teaching Learning Centre
A Centre of MHRD, Govt. of India
under
Pandit Madan Mohan Malaviya National Mission on Teachers and Teaching
(PMMMNMTT)
Sri Guru Tegh Bahadur Khalsa College
University of Delhi, Delhi, India
Email id: mhrdnrc.chemistry@gmail.com
 ONLINE REFRESHER COURSE IN CHEMISTRY FOR HIGHER EDUCATION FACULTY (2018)
@ SWAYAM.GOV.IN
________________________________________________________________________

CREDITS

CORE TEAM Name & Institution

Coordinator, Dr. (Mrs.) Vimal Rarh

NRC of Chemistry Coordinator, National Resource Centre of Chemistry
Project Head & Joint Director, Guru Angad Dev Teaching Learning Centre (GAD-TLC)
Senior Asst. Professor, Department of Chemistry
SGTB Khalsa College, University of Delhi
Chairman, Prof. A K Bakhshi
NRC of Chemistry Vice Chancellor, PDM University
Ex-Chair Professor, Dept. of Chemistry, University of Delhi
Chairman, and National Resource Centre of Chemistry of MHRD
Chairman, Guru Angad Dev Teaching Learning Centre (GAD-TLC) of MHRD
Director Dr. Jaswinder Singh
Director, Guru Angad Dev Teaching Learning Centre (GAD-TLC)
Principal, SGTB Khalsa College, University of Delhi
Module Contributors Name & Institution

Author Prof. A.K. Bakhshi

Vice Chancellor, PDM University
Ex-Chair Professor, Dept. of Chemistry, University of Delhi
Chairman, and National Resource Centre of Chemistry of MHRD
Chairman, Guru Angad Dev Teaching Learning Centre (GAD-TLC) of MHRD

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1. Introduction

While studying chemistry one comes across many concepts. A good understanding
of all these concepts is very essential if you want to excel both as a teacher as well
as researcher. However, our experience shows that there are many concepts about
which there are some doubts to the learners or there are some confusions. So in
the modules entitled “ChemMisconception” in all refresher programs in chemistry,
we will be talking about some common misconceptions in chemistry. The purpose
will be to highlight the misconception and remove the doubts or confusions there in .

2. What is pH?

The word pH stands for “power of hydrogen”. This term was coined by Danish
biochemist Sorenson in the year 1906. pH is always in the context of an aqueous
solution. pH for an aqueous solution is a measure of its acidity or basicity. pH is a
numerical scale whose range varies from 0 to 14 at 25oC.

So at 25oC, if pH is 7 for an aqueous solution it will be neutral; and if the pH is less

than seven it will be acidic; and for pH more than seven the solution will be basic.

3. What is the misconception about pH?

The pH of a solution is expressed mathematically as logarithm of the inverse of the

hydrogen ion or hydronium ion concentration.
!
𝑝𝐻 = log!" = − log!" 𝐻 !
!!

One can use hydrogen ions or hydronium ions interchangeably

So the misconception is that in this definition of pH the concentration of hydrogen
ions has units; normally these are moles per litre and here one is then taking
logarithm of a quantity which has got units. That’s the real problem - logarithm is
always taken of a number, one cannot take logarithm of a dimensional quantity. So
the question is how does one explain that or how does one account for that.
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One needs to know that logarithm is defined for a number (a constant numeric
value without units or dimensions) but here we express logarithm of a concentration
term (with units). And this concentration refers to the physical amount present in the
solution. It is usually measured in grams or moles per unit volume and can be easily
calculated.
A more precise definition of pH is:
!
𝑝𝐻 = log!" ! = −𝑙𝑜𝑔!" (𝑎! ! )
!!

where 𝑎! ! refers to the hydrogen ion activity in the solution.

This activity is an effective concentration of hydrogen ions, rather than the true
concentration. The activity of an ion is expressed as product of concentration (𝑐)
and activity coefficient (𝛾).
𝑎 = 𝛾. 𝑐
This activity coefficient is the correction factor based on thermodynamic
measurements and its value depends on (a) concentration of ions. (b) charge of the
ions and (c) diameter of the ions.
The activity coefficient is a dimensionless quantity. So, to make activity
dimensionless (as is the convention), the concentration of the ion is divided by the
standard amount i.e., concentration 𝑐 ° = 1𝑚𝑜𝑙/𝑑𝑚!

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Actual definition still involves activity; so this is one point which one needs to be very clear
about and one can see that for dilute aqueous solution, once gamma is one, pH is equal to
minus log activity of hydrogen ions and activity is now replaced by concentration of
hydrogen ions.
For dilute aqueous solutions, the pH varies from zero to fourteen as shown below:

The range of the concentration of hydrogen ions correspondingly is from 1 M to 1-14 M. As

a matter of fact, 10-14 is also the ionic product of water. When the solution is 1M, pH is
equal to zero and when the solution is 10-14 M, pH is equal to 14. Hence the pH range
varies between 0 to 14.

4. Can pH be negative?

Is negative pH for any aqueous solution possible? Yes, in principle it is possible but
negative pH has only a theoretical significance.
How does negative pH come?
From the equation for pH for any solution, which is having concentration of hydrogen ions
greater than 1M shall always have negative pH.
Examples:

For 2 M HCl,

For 12 M HCl,

Negative pH though theoretically possible, cannot be verified experimentally in the

laboratory.

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5. What is the pH of 10-8 M HCl ?

The following calculation, by directly putting value of concentration of hydrogen ions

is wrong:

The pH of an acidic solution can’t be 8!

To solve this, one needs to consider the hydrogen ions coming from water also, as
shown below:

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6. Variation of pH with temperature

Once the temperature changes, pH will change because the ionic product of water
will change.
At 25oC, Kw is 10-14 and since Kw is the product of the concentration of H+ ion and
product of concentration of OH- ion, it will come out to be seven; pOH will be seven
and pKw which is the sum total of pH and pOH that will come out to be fourteen.
At lower temperature, e.g., at 0oC, the ionic product decreases, that means on
lowering the temperature the ionization of water decreases. So we have less
concentration of H+ ions, less concentration of OH- ions and hence the pH
increases to 7.47; pOH also becomes 7.47. Here, pKw becomes 14.94 (please see
the Table below).
At higher temperature, e.g., 50oC, Kw increases; that means more water has
ionized. Hence pH of neutral water decreases to 6.63 and pOH is also 6.63; pKw
becomes 13.26.
When we say that pH of pure water is 7, this is only applicable at 25oC temperature.
pH of pure water will decrease as the temperature will increase.

7. Summary

• One cannot take logarithm of a dimensional quantity

!
• Precise definition of pH: 𝑝𝐻 = log!" ! = −𝑙𝑜𝑔!" (𝑎! ! )
!!
• Negative pH though theoretically possible, cannot be verified experimentally
in the laboratory.
• Once the temperature changes pH changes because the ionic product of
water changes.
• pH of pure water decreases as the temperature increases and vice-versa.

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Reference Material
• https://www.acs.org/content/dam/acsorg/pressroom/podcasts/ph-test-strips-
activity.pdf
• https://wrrc.umass.edu/research/projects/acid-rain-monitoring-
project/analysis-method-ph-and-alkalinity

Web-Links
• https://www.growthtechnology.com/growtorial/what-is-the-ph-value/
• http://academic.brooklyn.cuny.edu/biology/bio4fv/page/ph_def.htm
• http://hyperphysics.phy-astr.gsu.edu/hbase/Chemical/ph.html
• https://www.sciencebuddies.org/science-fair-projects/references/acids-
bases-the-ph-scale

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