Dissociation Constant: (Item No.: P3031101)
Dissociation Constant: (Item No.: P3031101)
Dissociation Constant: (Item No.: P3031101)
Sheet
Printed: 03/12/2017 13:50:14 | P3031101
Keywords:
True and potential electrolytes, Strong and weak acids, Law of mass action, Dissociation constants and pKa values, Henderson-Hasselbach
equation, UV-visible spectrometry, Lambert-Beer’s Law, Photometry
Introduction
Short description
Principle
The coloured indicator thymol blue is a weak acid that is partially dissociated in aqueous solution, whereby non-ionized
and ionized forms show absorption maximums at different wavelengths in the visible range. Photometric measurements in
the visible spectral range can therefore be used to advantage to determine the position of the Ka and pKa values of the
indicator which characterize dissociation equilibrium.
Equipment
Tasks
Experimentally determine the extinction (absorbance) of an aqueous solution of thymol blue (thymolsulphonephthalein) in dilute
HCl, NaOH and a buffer of known pH value as a function of wavelength between 400 and 700 nm at constant concentration and
constant temperature. Calculate the dissociation constant (indicator constant) Ka from the measurement results.
Read off the extinction values from the spectra displayed by the monitor in 5 nm steps and plot a graph of them as a
function of wavelength.
Fig. 1
Results
The absorption spectra recorded at T = 299 K are shown in Fig. 2. Absorption spectra of thymol blue (c0 = 2 · 10-5 mol · l-1) in 1 ·
10-4 molar HCl ( ) 1 · 10-3 molar NaOH ( ) and a buffer solution of pH = 9.00 ( ) at T = 299 K.
Fig. 2
Note
The graphical evaluation of the measured values can be very easily carried out by means of ‘Measure’ software. A
downloadfile of this software is available as freeware for use in evaluating and graphically representing measured values under
URL ”www.phywe.com“. Fig. 2 was created by this software.
Evaluation
The coloured indicator thymol blue, which is used in analytical practice, is present in aqueous solutions in the partly
dissociated weak acid form:
The position of the dissociation equilibrium is quantitatively characterized by the acid or indicator constant Ka or the pKa value
derived from it:
(1)
(2)
From (1), considering formulation (2) and the analogue definition of the pH value and taking logarithms, we obtain the
Henderson-Hasselbach equation (3). This describes, at a given acid strength, the connection between the pH value and the
composition (cHA / cA-) of the buffer system, and so the share of the two forms in the total concentration c0 of the weak acid.
(3)
(4)
We so have, in the acid form (1 · 10-4 molar HCl, pH = 4 pKa), practically only the non-ionized acidic form HA, so that
(4) becomes (4.1).
(4.1)
In contrast to this, in basic mileau (1 · 10-3 molar NaOH, pH = 11 pKa), equilibrium is shifted almost completely in the
direction of the ionized salt form A-, and we have
(4.2)
In buffered solutions of pH 9 pKa the ionized and non-ionized forms are present in practically the same concentration.
These equilibrium concentrations, and so the constants Ka and pKa, for thymol blue, can be advantageously measured via
photometric measurements as, because of their different atomic structures, the acid and salt forms give different absorption
spectra which cross each other at an isosbestic point (Fig. 2).
The HA form that exists alone in acidic solutions absorbs in the blue spectral range ( 430 nm) and appears as the
complementary colour, yellow. On the other hand, the blue salt form A- that exists alone in basic solutions absorbs in the yellow
spectral range ( 595 nm). In buffered solutions a mixed colour is observed because of the existence of HA and A-, both
of which absorb in the visible spectral range.
In analytical practice, the intensity of absorption is usually quantified by the extinction that is defined in equation (5):
(5)
Its dependence on the concentration ci of an absorbing substance i and the layer thickness d at constant wavelength is given by
the Lambert-Beer law:
(6)
which, with the simultaneous presence of two absobing substances (here HA and A-), takes on the form:
(6.1)
In acidic solution (cA- = 0, cHA = c0) or basic solution (cHA = 0, cA- = c0), equation (6.1) can be simplified to (6.1.1) and (6.1.2).
(6.1.1)
(6.1.2)
(7)
Equation (7) is one possibility for calculating the concentration of the ionized form A-. In this equation, represents the
extinction of the buffered solution that should be measured at a wavelength ( ) that is sufficiently well away from the
isosbestic point. The extinction coefficients and can be calculated from equations (6.1.1) and (6.1.2) from the
extinctions of the acid and basic thymol blue solutions of c0 = 3 · 10-5 molar at the same wavelength. With cA- known, then cHA
is accessible via equation (4). Insertion of the values for cA- and cHA the concentration determined by the buffer of c = 1 · 10-9
mol · l-1 in the law of mass action (1) gives the indicator constant Ka.
For the compound examined here, an alternative evaluation procedure can be used. As at wavelengths above 625 nm (Fig.
2) practically only the conjugated base A- absorbs ( ), equation (6.1) changes to:
(6.1.3)
The quotient from the relationships (6.1.3) and (6.1.2) is, according to definition, equal to the degree of dissociation ,
(8)
This can be calculated from the extinctions and measured in buffered solution or NaOH at constant wavelength.
The indicator constant Ka is then accessible from the relationship derived from the law of mass action (1) and the relationships
(4) and (8):
(9)
The negative decadic logarithm of its numerical value is, according to definition (2), equal to the pKa value.