Acid Dissociation Constant of Methyl Red

Abstract- This experiment aims to observe the of frequency or wavelength or pattern of dark lines or bands,
absorptivity of Methyl Red in the aid to calculate for due to its interaction with a sample. The sample absorbs
dissociation constant. This experiment chooses Methyl energy from the radiating field. The intensity of the
red as the system of interest due to its known distinct absorption varies as a function of frequency, and this
characteristics for the acidic and basic media. This variation is the absorption spectrum. Absorption
experiment is carried through a direct spectroscopy is a tool to determine the presence of a
spectrophotometric. This is performed in both acidic and particular substance in a sample and, in many cases, to
basic media and was allowed to be scanned through the
quantify the amount of the substance
wavelengths 400-600nm. The peaks (maximum
present. Infrared and ultraviolet-visible spectroscopy are
wavelength absorption) for each were then used as the
particularly common in analytical applications. [1]
reference wavelengths to which the buffered solutions
were allowed to be observed. Molar absorptivity of the From the use of spectrophotometer to determine the
increments of the acidic and basic MR were then graphed concentrations of a substance and using the absorbance
and determined through the respective slopes of observed measurements made by the instrument, the concentration of a
from each of the peaks. At the end of the experiment, it solution can also be calculated using Beer’s law. [3] For each
was found that the Methyl red to have a pKa value of wavelength of light passing
4.5194 with a relative error to that of the literary value to
through the spectrometer, the
have 9.613% and an Acid Dissociation constant of 3.02 x
intensity of the light passing
𝟏𝟎−𝟓 .
through the reference cell is
Keywords- dissociation, attenuation, absorptivity, measured. This is usually referred to as Io. The intensity of
frequency, wavelength the light passing through the sample cell is also measured for
that wavelength given the symbol, I. [4]
I. INTRODUCTION
An acid dissociation constant, Ka, is
a quantitative measure of the strength of an acid in solution. Another important point is the relationship between
[`1]
The dissociation constant in the context of acid-base pH and the pKa of an acid as accounted in the Henderson-
reactions is usually written as a quotient of Hasselbach equation above.
the equilibrium concentrations as stated by the law of mass
action: II. EXPERIMENTAL
[ A][ H ]
K .
[ HA] The experiment has four parts: the preparation of solutions,
The Ka value can also be expressed in the the determination of the absorption maxima, checking with
Henderson-Hasselbach equation: beer’s law, and the determination of the acid dissociation
[ A] constant.
pK  pH  log .
[ HA] On the first part, the standard solution of methyl red is made
The larger the value of pKa, the smaller the extent of by adding 2mL of the stock solution to 25 mL of 95% ethanol
dissociation. [2] In relation to this, this experiment aims to and diluting it to 50 mL of water using pipets and volumetric
determine the pKa of methyl red by measuring absorbance flasks. The following solutions are also made: 250 mL of
spectra as a function of pH. Methyl red provides a 0.04 M NaCH3COO, 100 mL of 0.01 M NaCH3COO, 100
particularly good system to study acid-base equilibrium since mL of 0.01 M NaCH3COOH, 100 mL of 0.02 M CH3COOH,
both its acid and base forms have strong absorption peaks in 100 mL of 0.1 M HCl, and 100 mL of 0.01 M HCl.
the visible portion of the spectrum. [5] While in determining
these absorption peaks, a spectrophotometer will be used. On the second part, solutions A and B are made. For solution
A where the methyl red present is on its acid form, a mixture
Absorption spectroscopy refers
of 10 mL standard methyl red solution and 10 mL of 0.1 M
to spectroscopic techniques that measure
HCl is diluted to 100 mL. For solution B, methyl red on base
the absorption of radiation, as a function
form, a mixture of 10 mL standard methyl red solution and
 25 mL of 0.04M NaCH3COO is also diluted to 100 mL. The
absorption spectrum of methyl red on both solutions were
determined in the spectrophotometer with the range of 350 to
600 nm using distilled water as the reference cell.
On the third part, portions of solutions A and B are diluted to
0.75, 0.50, 0.25 times their initial concentrations using 0.01
M HCl and 0.01 M NaCH3COO. Then the absorbance of
each solution, water as blank, is measured at their wavelength
maximum (λA and λB).
Lastly, a series of solutions added by various amounts of 0.02
M acetic acid to constant amounts of solution B buffered with
0.04 M NaCH3COO solution. The absorbance of the
solutions is then measured at λA and λB, and pH values are
also determined using a standardized pH meter.
III. RESULT AND DISCUSSION
The objectives of this experiments are to determine
the wavelength at which HMR and 𝑀𝑅− exhibit absorption
maxima, to verify Beer’s Law for HMR and 𝑀𝑅− and
determine their absorbance indices at wavelength maximum,
to determine the relative amounts of HMR and 𝑀𝑅 − present
in the solution at a function of pH and to determine the acid
dissociation constant at methyl red. Two solutions of
Standard Methyl Red were prepared where methyl red is in
acid form (Solution A), HMR and in basic form (Solution B),
𝑀𝑅− respectively. Absorption Spectrum of Methyl Red in
both solution was measured between the wavelengths 400 nm
– 600 nm. Graph 1 shows the absorbance versus wavelength
for both the acid and base forms.
1.4
1.2
1 HMR, 0.138 for λB, HMR, 0.048 for λA, MR and 0.5 for λB,
0.8
Absorbance
A
0.6
B properties of the material through which the light is
0.4
0.2
0
0 200 400 600 800
Wavelength (nm)
Graph 1. The Absorbance against the wavelength for both
Solution A and B
The maximum absorbance for Solution A (λA) is
1.23 measured at wavelength 520 nm while the maximum
absorbance for Solution B (λB) is 0.505 measured at
wavelength 429 nm. As shown in the graph above, the
spectra of both forms of Methyl Red intersects at around
wavelength of 463 nm and absorbance of 0.424. This
intersection point is called the isosbestic point. An isosbestic
point is a specific wavelength, wavenumber or frequency at
which the total absorbance of a sample does not change
during a chemical reaction or a physical change of the
sample. [1] The observation of isosbestic points indicates that
the stoichiometry of the reaction remains unchanged during
the chemical reaction or the physical change of the sample,
and that no secondary reactions occur during the considered
time range and its existence does not prove that the reaction
is a quantitative conversion of one species into a unique other
species or that an equilibrium exists between only two
species contrary to widely accepted idea. [2] Absorbance of
relative concentrations of methyl red for both forms were
measured at both maximum wavelength of methyl red (λA
and λB). Graph 2 shows the absorbance versus concentration
1
0.9
λA,
0.8
HMR
0.7
Absorbance
0.6 λB,
HMR
0.5
0.4 λA,
0.3 MR
0.2
λB,
0.1 MR
0
0 0.2 0.4 0.6 0.8
Concentration
of methyl red for each of the forms.
Graph 2. The Absorbance against relative concentrations for
both Solution A and B
The slopes of the respective lines are folloing; 1.16 for λA,
MR. These slopes are the molar absorptivity of the methyl
red. The Beer’s Law relates the attenuation of light to the
traveling.[3]Molar absorptivity or molar attenuation
coefficient is a measurement of how strongly a chemical
species attenuates light at a given wavelength. It is
an intrinsic property of the species. The SI unit of molar
attenuation coefficient is the square metre per mole (m2/mol),
but in practice, it is usually taken as the M−1⋅cm−1 or the
L⋅mol−1⋅cm−1.[4] It is a constant for each species and
wavelength.
In determining the relative amounts of HMR and
−
𝑀𝑅 present in the solution at a function of pH, series of
solutions of various amounts of 0.02 M Acetic Acid was
mixed with Solution B buffered with 0.04 M Sodium Acetate
Solution. pH values and absorbance at λA and λB were
measured. Table 1 shows the tabulation of 𝐴𝐴 , 𝐴𝐵 , pH and
volume of 0.02 Acetic Acid.
Table 1. Tabulation of 𝐴𝐴 , 𝐴𝐵 , pH and volume of 0.02 Acetic having a slope equal to that of the molar absorptivity of
Acid. methyl red. The slopes were as follows (having Acid MR
first at wavelength A then B form then Basic MR follows):
V of AcOH 𝐴𝐴 𝐴𝐵 , pH 1.16, 0.138, 0.048, 0.5. This indicates the strength a chemical
5 mL 0.463 0.121 4.9 specie attenuates light in a certain wavelength.
10 mL 0.190 0.107 4.6
15 mL 0.129 0.079 4.2 -it is found to that absorbance at wavelengths A and B are
20 mL 0.124 0.074 4.1 just the additive sums of the absorbance in line with the
amounts present of HMR and MR.

Using the obtained data, molar bsorptivity and Eq. -The pKa was calculated to be 4.5194 having relative error of
9.613% to that of the known pKa for MR. further, the acid
3.3 & 3.4, relative amounts of HMR and 𝑀𝑅 − . (refer to
appendix for calculations). Eq. 3.3 & 3.4 imply that the dissociation constants was the latter found to be 3.02 x 10−5 .
observed absorbance at λA and λB are the simple additive
sums of the absorbance due to HMR and 𝑀𝑅 − . Table 1
shows the Tabulation of relative amounts of HMR and 𝑀𝑅− , REFERENCES
volume of 0.02 Acetic Acid and pKa.
FOR INTRODUCTION SOURCES
−
Table 2. Tabulation of HMR and 𝑀𝑅 ,pKa and volume of
[1] Acid Dissociation & Absorption Spectroscopy:
0.02 Acetic Acid.
https://en.wikipedia.org/wiki/
V of AcOH [HMR] [MR] pKa [2]BoundlessChemistry. https://www.boundless.com/chemist
ry/textbooks/boundless-chemistry-textbook/acids-and-bases-
5 mL 0.3936 0.1334 5.3700 15/acids-and-bases-107/acid-dissociation-constant-ka-452-
10 mL 0.1567 0.1707 4.5628 10532/
15 mL 0.1059 0.1288 4.1150 [3]
20 mL 0.1019 0.1199 4.0296 http://www.chem.ucla.edu/~gchemlab/colorimetric_web.htm
[4] Beer’s Law:
http://www.chemguide.co.uk/analysis/uvvisible/beerlambert.
pKa is obtained using Henderson Hasselbach html
equation. The average pKa 4.5194. It has 9.613% error with [5] Acid Dissociatipn Constant of Methyl Red- 2017.ppt
respect to the theoretical pKa of methyl red (refer to appendix
for calculation). pKa is simply equal to the negative FOR RESULTS AND DISCUSSION SOURCES
logarithm of the acid dissociation constant. Therefore, the
[1] Isosbestic Point. Retrieved from:
acid dissociation constant (Ka) is 3.02 x 10−5 .
https://en.wikipedia.org/wiki/Isosbestic_point.

[2] Significance of Isosbestic Point. Retrieved from:

IV. ERROR ANALYSIS https://goldbook.iupac.org/I03310.html

A major error contributor in this experiment as observed by [3] Beer’s Law. Retrieved from:
the people conducting the experiment was the inaccuracy of https://en.wikipedia.org/wiki/Beer%E2%80%93Lambert_law
the pH meter used. Another sources of error could be human
errors such as inconsistent approximation in terms of making
solutions in viewing the meniscus of a measuring apparatus
(e.g, graduated cylinder, pipets).. Other relative sources of
error for this experiment are number bias and personal
judgement.

V. CONCLUSION

In this experiment the following conclusions were drawn and

were based entirely from the data gathered:

-The maximum absorbance for the acidic methyl red solution

was found to be 1.23 and for that of the basic methyl red
solution was 0.505 and were measured between 400-600 nm
wavelengths. The said peaks for each solution were
determined to be at 520 nm and 429 nm respectively.

-Each form having different concentrations were run through

both maximum wavelength of methyl red and was graphed to