Professional Documents
Culture Documents
Lab 9 2020 2
Lab 9 2020 2
Lab 9 2020 2
pH measurement
Key words:
pH, pOH, acids, bases, buffers, electrodes, buffer capacity.
Literature:
J. Crowe, T. Bradshaw, P. Monk, Chemistry for the Biosciences. The essential concepts,
Oxford University Press, 2006; Chapter 17, 515 – 545.
J. Brady, N. Jespersen, A. Hysop, Chemistry, International Student Version, 7thed. Wiley,
2015, Chapter 16, 762 – 798.
P. Monk, Physical Chemistry, Wiley 2004, Chapter 6, 233- 276.
Theoretical background
Introduction
In a solution pH approximates but is not equal to p[H], the negative logarithm (base 10) of the
molar concentration of dissolved hydronium ions (H3O+); a low pH indicates a high
concentration of hydronium ions, while a high pH indicates a low concentration.
Crudely, this negative of the logarithm matches the number of places behind the decimal
point, so for example 0.1 molar hydrochloric acid should be near pH 1 and 0.0001 molar HCl
should be near pH 4 (the base 10 logarithms of 0.1 and 0.0001 being −1, and −4,
respectively).
Pure (de-ionized) water is neutral, and can be considered either a very weak acid or a very
weak base (center of the 0 to 14 pH scale), giving it a pH of 7 (at 25 C (77°F)), or 0.0000001
M H+. For an aqueous solution to have a higher pH, a base must be dissolved in it, which
binds away many of these rare hydrogen ions. Hydrogen ions in water can be written simply
as H+ or as hydronium (H3O+) or higher species (e.g. H9O4+) to account for solvation, but all
describe the same entity.
Lab.9. pH measurement
Most of the Earth's freshwater surface bodies are slightly acidic due to the abundance and
absorption of carbon dioxide; in fact, for millennia in the past most freshwater bodies have
long existed at a slightly acidic pH level.
However, pH is not precisely p[H], but takes into account an activity factor. This represents
the tendency of hydrogen ions to interact with other components of the solution, which affects
among other things the electrical potential read using a pH meter. As a result, pH can be
affected by the ionic strength of a solution – for example, the pH of a 0.05 M potassium
hydrogen phthalate solution can vary by as much as 0.5 pH units as a function of added
potassium chloride, even though the added salt is neither acidic nor basic.
History
The concept of p[H] was first introduced by Danish chemist Søren Peder Lauritz Sørensen at
the Carlsberg Laboratory in 1909 and revised to the modern pH in 1924 after it became
apparent that electromotive force (emf) in cells depended on activity rather than concentration
of hydrogen ions. In the first papers, the notation had the H as a subscript to the lower-case p,
like so: pH.
It is unknown what the exact definition of 'p' in pH is. A common definition often used in
schools is "percentage". However some references suggest the p stands for “Power”, others
refer to the German word “Potenz” (meaning power in German), still others refer to
“potential”. Jens Norby published a paper in 2000 arguing that p is a constant and stands for
“negative logarithm”; H then stands for Hydrogen. According to the Carlsberg Foundation pH
stands for "power of hydrogen". Other suggestions that have surfaced over the years are that
the p stands for puissance (also meaning power but then the Carlsberg Laboratory was French
speaking) or that pH stands for the Latin terms pondus Hydrogenii or potentia hydrogenii. It is
also suggested that Sørensen used the letters p and q (commonly paired letters in
mathematics) simply to label the test solution (p) and the reference solution (q).
Lab.9. pH measurement
Mathematical definition
(1)
Activity has a sense of concentration; however, activity is always less than the concentration
and is defined as a concentration (mol/L) of an ion multiplied by activity coefficient. The
activity coefficient is a number between 0 and 1 and it depends on many parameters of a
solution, such as nature of ion, ion force, temperature etc.
Quite often glass electrode is combined with the reference electrode and a temperature sensor
in one body. The glass electrode relatively good (95 - 99.9%) follows the Nernst equation:
(2,3)
where E is a measured potential, E0 is the standard electrode potential, that is, the electrode
potential for the standard state in which the activity is one. R is the gas constant, T is the
temperature in Kelvins, F is the Faraday constant and n is the number of electrons transferred
(ion charge), one in this instance. The electrode potential, E, is proportional to the logarithm
of the hydrogen ion activity (or concentration at first approximation).
Lab.9. pH measurement
This definition, by itself, is wholly impractical, because the hydrogen ion activity is the
product of the concentration and an activity coefficient. To get proper results, the electrode
must be calibrated using standard solutions of known activity.
Measurement of extremely low pH values, such as some very acidic mine waters, requires
special procedures. Calibration of the electrode in such cases can be done with standard
solutions of concentrated sulfuric acid, whose pH values can be calculated with using Pitzer
parameters to calculate activity coefficients.
pOH
So, at room temperature pOH ≈ 14 − pH. However this relationship is not strictly valid in
other circumstances, such as in measurements of soil alkalinity.
Application
Pure (neutral) water has a pH around 7 at 25 °C (77 °F); this value varies with temperature.
When an acid is dissolved in water the pH will be less than 7 (if at 25 °C (77 °F)) and when a
base, or alkali is dissolved in water the pH will be greater than 7 (if at 25 °C (77 °F)). A
Lab.9. pH measurement
solution of a strong acid, such as hydrochloric acid, at concentration 1 mol dm−3 has a pH of
0.
A solution of a strong alkali, such as sodium hydroxide, at concentration 1 mol dm−3 has a pH
of 14. Thus, measured pH values will mostly lie in the range 0 to 14. Since pH is a
logarithmic scale a difference of one pH unit is equivalent to a tenfold difference in hydrogen
ion concentration.
Because the glass electrode (and other ion selective electrodes) responds to activity, the
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.
Universal indicator consists of a mixture of indicators such that there is a continuous color
change from about pH 2 to pH 10. Universal indicator paper is simple paper that has been
impregnated with universal indicator.
A solution whose pH is 7 (at 25 °C (77 °F)) is said to be neutral, that is, it is neither acidic nor
basic. Water is subjected to a self-ionization process.
H2O H+ + OH−
The dissociation constant, KW, has a value of about 10−14, so in neutral solution of a salt both
the hydrogen ion concentration and hydroxide ion concentration are about 10−7 mol dm−3.
The pH of pure water decreases with increasing temperatures. For example, the pH of pure
water at 50 °C is 6.55. Note, however, that water that has been exposed to air is mildly acidic.
This is because water absorbs carbon dioxide from the air, which is then slowly converted
into carbonic acid, which dissociates to liberate hydrogen ions:
Lab.9. pH measurement
In the case of a strong acid, there is complete dissociation, so the pH is simply equal to minus
the logarithm of the acid concentration.
For example, a 0.01 molar solution of hydrochloric acid has a pH = −log(0.01), that is, pH =
2.
where c0 is the concentration of the acid. This is equivalent to Burrows' weak acid pH
equation
(7)
A more general method is as follows. Consider the case of dissolving a weak acid, HA, in
water. First write down the equilibrium expression.
HA A− + H+
(8)
The analytical concentration of the two reagents, CA for [A−] and CH for [H+] must be equal to
the sum of concentrations of those species that contain the reagents. CH is the concentration of
added mineral acid.
(11)
(12)
(13)
This method can also be used for polyprotic acids. For example, for the diprotic acid oxalic
acid, writing A2− for the oxalate ion,
Following the same procedure of substituting from the first equation into the second, a cubic
equation in [H+] results. In general, the degree of the equation is one more than the number of
ionisable protons. The solution of these equations can be obtained relatively easily with the
aid of a spreadsheet such as EXCEL or Origin. The pH always has an amount of fractional
figures equal to the amount of significant figures of the concentration.
Lab.9. pH measurement
pH in nature
pH-dependent plant pigments that can be used as pH indicators occur in many plants,
including hibiscus, marigold, red cabbage (anthocyanin), and red wine.
Living systems
The pH of different cellular compartments, body fluids, and organs is usually tightly regulated
in a process called acid-base homeostasis.
Compartment pH pH
Gastric acid 1
Lysosomes 4.5
Granules of chromaffin cells 5.5
Human skin 5.5
Urine 6.0
Neutral H2O at 37 °C 6.81
Cytosol 7.2
Cerebrospinal fluid (CSF) 7.3
Blood 7.34–7.45
Mitochondrial matrix 7.5
Pancreas secretions 8.1
Lab.9. pH measurement
The pH of blood is usually slightly basic with a value of pH 7.365. This value is often referred
to as physiological pH in biology and medicine.
Plaque can create a local acidic environment that can result in tooth decay by
demineralisation.
Enzymes and other proteins have an optimum pH range and can become inactivated or
denatured outside this range.
The most common disorder in acid-base homeostasis is acidosis, which means an acid
overload in the body, generally defined by pH falling below 7.35
In the blood, pH can be estimated from known base excess (be) and bicarbonate concentration
(HCO3) by the following equation:
(16)
pH meter
The probe
The pH probe measures pH as the activity of hydrogen ions surrounding a thin-walled glass
bulb at its tip. The probe produces a small voltage (about 0.06 volt per pH unit) that is
measured and displayed as pH units by the meter. For more information about pH probes, see
glass electrode.
For very precise work the pH meter should be calibrated before each measurement. For
normal use calibration should be performed at the beginning of each day. The reason for this
is that the glass electrode does not give a reproducible e.m.f. over longer periods of time.
Calibration should be performed with at least two standard buffer solutions that span the
range of pH values to be measured. For general purposes buffers at pH 4 and pH 10 are
acceptable. The pH meter has one control (calibrate) to set the meter reading equal to the
Lab.9. pH measurement
value of the first standard buffer and a second control (slope) which is used to adjust the meter
reading to the value of the second buffer. A third control allows the temperature to be set.
Standard buffer sachets, which can be obtained from a variety of suppliers, usually state how
the buffer value changes with temperature.
The calibration process correlates the voltage produced by the probe (approximately 0.06
volts per pH unit) with the pH scale. After each single measurement, the probe is rinsed with
distilled water or deionized water to remove any traces of the solution being measured, blotted
with a clean tissue to absorb any remaining water which could dilute the sample and thus alter
the reading, and then quickly immersed in another solution.
When not in use, the glass probe tip must always be kept wet to avoid the pH sensing
membrane dehydration and the subsequent dysfunction of the electrode.
A glass electrode alone (i.e., without combined reference electrode) is typically stored
immersed in an acidic solution of around pH 3.0. In an emergency, acidified tap water can be
used, but distilled or deionized water must never be used for longer-term probe storage as the
relatively ionless water "sucks" ions out of the probe membrane through diffusion, which
degrades it.
Combined electrodes (glass membrane + reference electrode) are better stored immersed in
the bridge electrolyte (often KCl 3 M) to avoid the diffusion of the electrolyte (KCl) out of
the liquid junction.
Types of pH meters
pH meters range from simple and inexpensive pen-like devices to complex and expensive
laboratory instruments with computer interfaces and several inputs for indicatorerature
measurements be entered to adjust for the slight variation in pH caused by temperature.
Specialty meters and probes are available for use in special applications, harsh environments,
etc.
Lab.9. pH measurement
Glass electrode
A glass electrode is a type of ion-selective electrode made of a doped glass membrane that is
sensitive to a specific ion. It is an important part of the instrumentation for chemical analysis
and physico-chemical studies. In modern practice, widely used membranous ion-selective
electrodes (ISE, including glasses) are part of a galvanic cell. The electric potential of the
electrode system in solution is sensitive to changes in the content of a certain type of ions,
which is reflected in the dependence of the electromotive force (EMF) of galvanic element
concentrations of these ions.
History
F. Haber and Z. Klemensiewicz [Polish scientist] publicized on January 28, 1909 results of
their research on the glass electrode in The Society of Chemistry in Karlsruhe (first
publication — The Journal of Physical Chemistry by W. Ostwald and J. H. van 't Hoff) —
1909).
Legend:
Lab.9. pH measurement
Applications
Glass electrodes are commonly used for pH measurements. There are also specialized ion
sensitive glass electrodes used for determination of concentration of lithium, sodium,
ammonium, and other ions. Glass electrodes have been utilized in a wide range of
applications — from pure research, control of industrial processes, to analyze foods,
cosmetics and comparison of indicators of the environment and environmental regulations: a
microelectrode measurements of membrane electrical potential of a biological cell, analysis of
soil acidity, etc.
The Saturated calomel electrode (SCE) is a reference electrode based on the reaction between
elemental mercury and mercury(I) chloride. The aqueous phase in contact with the mercury
and the mercury(I) chloride (Hg2Cl2, "calomel") is a saturated solution of potassium chloride
in water. The electrode is normally linked via a porous frit to the solution in which the other
electrode is immersed. This porous frit is a salt bridge.
Theory of operation
where E0 is the standard electrode potential for the reaction and aHg is the activity for the
mercury cation (the activity for a liquid of 1 Molar is 1). This activity can be found from the
solubility product of the reaction
By replacing the activity in the Nernst equation with the value in the solubility equation, we
get
The only variable in this equation is the activity (or concentration) of the chloride anion. But
since the inner solution is saturated with potassium chloride, this activity is fixed by the
solubility of potassium chloride. When saturated the redox potential of the calomel electrode
is +0.2444 V vs. SHE at 25 °C, but slightly higher when the chloride solution is less than
saturated. For example, a 3.5M KCl electrolyte solution increases the reference potential to
+0.250 V vs. SHE at 25 °C, and a 0.1 M solution to +0.3356 V at the same temperature.
Application
This electrode and the silver/silver chloride reference electrode work in the same way. In both
electrodes, the activity of the metal ion is fixed by the solubility of the metal salt.
Lab.9. pH measurement
The calomel electrode contains mercury, which poses much greater health hazards than the
silver metal used in the Ag/AgCl electrode.
The standard hydrogen electrode (abbreviated SHE), also called normal hydrogen electrode
(NHE), is a redox electrode which forms the basis of the thermodynamic scale of oxidation-
reduction potentials. Its absolute electrode potential is estimated to be 4.44 ± 0.02 V at 25 °C,
but to form a basis for comparison with all other electrode reactions, hydrogen's standard
electrode potential (E0) is declared to be zero at all temperatures. Potentials of any other
electrodes are compared with that of the standard hydrogen electrode at the same temperature.
This redox reaction occurs at platinized platinum electrode. The electrode is dipped in an
acidic solution and pure hydrogen gas is bubbled through it. The concentration of both the
reduced form and oxidised form is maintained at unity. That implies that the pressure of
hydrogen gas is 1 bar and the activity of hydrogen ions in the solution is 1 molar. The activity
of hydrogen ions is their effective concentration, which is equal to the formal concentration
times the activity coefficient. Activity coefficients are close to 1.00 for very dilute water
solutions but are usually lower for more concentrated solutions. The Nernst equation should
be written as:
or
where:
Online pH calculator
http://www.webqc.org/phsolver.php
For solutions with ionic strengths of 0,1 M or less, the electrolyte effect is independent
Lab.9. pH measurement
EXPERIMENTAL PART
Equipment
• pH meter;
• solutions of different acids and bases
• solutions of acetic acid, ammonia
• solution different salts solution
Procedure
1.Measurement of pH of strong acids
Step 1.
Prepare 5 solutions of H2SO4 (concentration from 1.0 to 0.0001 M, according to data in Table
1) in the beakers of capacity 25 mL.
Step 2.
Insert the clean and dry electrode of the pH meter to selected solution (e.g. 0.0001M).
Step 3.
Record the values of pH in Table 1.
Step 4.
Clean the electrode of the pH meter with distilled water and dry it with tissue.
Step 5.
Repeat measurement procedure (steps 2-4) to remaining acid solution (e.g.0.001, 0.01, 0.1 and
1.0M)
Step 6.
Prepare 5 solutions of HCl (concentration from 0.0001 to 1.0 M, according to data in Table 2)
in the beakers of capacity 25 mL.
Step 7
Repeat steps 2-6. Report data in Table 2.
pH measured experimentally
pH measured experimentally
For salts with one strong and one weak component the best way of pH calculation it to treat
conjugate acid (or base) as the only source of H+ (or OH-) ions. For example, if we have
solution of salt of weak acid (with dissociation constant Ka) and strong base, reaction of
hydrolysis is
where
Starting from these equations we can calculate pOH and pH of the solution using method and
assumptions shown for weak acid and base. The same approach can be used for salt of strong
acid and weak base - just using the Ka constant for acid conjugate with weak base.
In the case of salt of weak acid and weak base situation is more complicated, but sometimes
we can get pretty good results assuming similar degree of both hydrolysis processes (as seen
above).
Let's say we have a solution of AB salt of weak acid and weak base of concentration C and
dissociation constants Ka and Kb. Our first assumption is that the hydrolysis is not too strong,
so that in the equilibrium [A-] = [B+] =C. If so, equations for Ka and Kb take forms
Multiplying:
and rearranging:
Please note that these Ka and Kb values are not related by KaKb=Kw, as they describe different
substances.
Now it is time for the second assumption - that degree of both hydrolysis reactions is similar,
so [HA]=[BOH]:
It gives concentration of HA which can be used for [H+] calculation. If equation above is
insert into
It is obtained:
Lab.9. pH measurement
or
Step 16.
Using the automatic dispenser add 0.25 mL of 0.5 M HCl to the test solution. (One pump of
the dispenser).
Step 17.
Mix well with the glass stirring rod and then measure the pH of the solution. Record data in
Table 6.
Step 18.
Discard the solution from the beaker into the waste bottle. Thoroughly rinse the beaker with
DI water and then dry the beaker.
Step 19.
Transfer 5 mL of the test solution [BUFFER pH 4 AND BUFFER pH 10] to another beaker
(use a graduated cylinder) and set aside.
Step 20.
To the remaining 5 mL portion of the test solution add 0.25 mL of 0.5 M NaOH (one pump
of the automatic dispenser).
Step 21
Lab.9. pH measurement
Mix well with the glass stirring rod and then measure the pH. Record data in Table 6
Step 22.
Discard the solution in the waste bottle. Thoroughly rinse the beaker with water and then dry
the beaker.