SPECTROPHOTOMETRIC DETERMINATION

DISSOCIATION CONSTANT OF METHYL RED

OF

THE

ACID

C.F. BATIFORRA
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMANQUEZON CITY, PHILIPPINES
DATE PERFORMED: MAY 2, 2015
INSTRUCTORS NAME: MARIEL CLORES

ABSTRACT
The experiment aimed to apply spectrophotometric concepts and beer's law in the
determination of the acid dissociation constant of methyl red. Methyl red is a commonly used indicator
because of it's property to change color within a range of pH. A spectrophotometer was used to
determine the absorptivity constants and subsequently, the concentrations of HMR and MR- in a twocomponent system. The dissociation constant was calculated by obtaining pH and concentration
values of the solutions. The calculated value for the pKa was 4.854 which had a 2.92% deviation from
the literature value of 5.00. We conclude that this method is effective in determining the
concentrations of unknown solutions containing two systems.

INTRODUCTION
Methyl red is a common indicator that
has an acidic form (HMR) and a basic form
(MR-). At pH 6.2 and above it appears as a
yellow solution and at pH 4.4 and below it
appears as a red solution.

The samples to be measured will have

two components meaning that the
absorbance of one species has an effect on the
absorbance of another species so we will
modify beer's law into the following
equations:

Our objective in this experiment is to

determine the dissociation constant of methyl
red
by
using
and
applying
spectrophotometric concepts. This will be
done by using the henderson-hasselbach
equation and by graphical analysis. By
measuring the pH and calculating the
respective concentrations of methyl red
components, we can calculate for the
dissociation constant, denoted by pKa.

Ahmr = hmr, hmrbchmr + hmr-, hmrbcmr(1)

Amr- = hmr, mr-bchmr + mr-, mr-bcmr- (2)

We
must
first
obtain
the
absorptivities of both species so two sets of
solutions containing only one species was
prepared. The absorbance of these solutions
were measured.

METHODOLOGY

The equations above can be used to

simtultaneously
compute
for
the
concentrations of both species through
systems
of
equations.
Once
the
concentrations of each species are obtained,
the dissociation can now be computed.

Preparation of Solutions

50mL of methyl red stock solutions

was prepared by dissolving 0.0572g of
methyl red into a 150mL beaker containing
30mL of 95% ethyl alcohol. The solution was
tranferred to a 50mL volumetric flask where
it was diluted to the mark. 50mL of methyl
red standard solution was prepared by
adding 25mL of 95% ethyl alcohol to 2.50mL
of the methyl red stock solution in a 50mL
volumetric flask. Dilute to mark.

*All volumes in mL

100mL of 0.040M sodium acetate

trihydrate was prepared by dissolving 0.544g
of sodium acetate in distilled water. 12.5mL
of this solution was diluted to prepare 50mL
of 0.010M.

The absorbance of the sample

solutions was then measured in the
spectrophotometer. The pH of solutions 7-10
was then measured using a pH meter.

50mL of working red methyl red

standard solutions were prepared each for
acidic and basic forms of methyl red. For the
acidic solution, 5.00mL methyl red standard
solution was pipeted into a 50mL volumetric
flask containing 5.00mL of 0.1M HCl solution.
Dilute to mark. The basic solution was
prepared by pipeting 5.00mL methyl red
standard solution into a 50mL volumetric
flask containing 12.50mL of 0.040M NaOAc
solution. Dilute to mark.
10 Sample solutions were prepared.
Solutions 1-3 only contained HMR, solutions
4-6 only contained MR- and solutions 7-10
contained both.

Determination of max wavelengths

The spectra of the HMR solution and
MR- solution was obtained by using a UV Vis
Spectrophotometer with water in the
reference cell. From this we can obtain the
wavelength of maximum absorption of both
solutions.

RESULTS AND DISCUSSION

Table 2.1 Conc vs. Absorbance
Solution
1
2
3
4
5
6

HMR

1
2
3

0.408
0.265
0.138

0.056
0.036
0.021

Solution

NaOAc

MR-

4
5
6

4.96
10.0
15.04

15.04
10.0
4.96

Solution

MR

HOAc

NaOAc

7
8
9
10

6.00
6.00
6.00
6.00

1.20
2.40
4.80
7.20

12.80
11.60
9.20
6.80

Absorbance

HCl

0.408
0.265
0.138
0.019
0.008
0.011

MR

Conc (M)

0.056
0.036
0.021
0.152
0.077
0.055

0.0001597
0.0001062
0.0000526
0.0001597
0.0001062
0.0000526

The figure below graphically shows the

concentrations of the solutions vs their
absorbances.

Table 1.1 Sample Solutions*

Solution

HMR

0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

0.0001

0.0002

Concentration
E HMR, HMR
E MR, MR

E HMR, MR
E MR, HMR

Figure 1.1 Molarity vs Absorbance plot

MR-

pH

7
8
9
10

3.96 x 10-6
7.78 x 10-6
1.81 x 10-5
2.84 x 10-5

6.44 x 10-5
5.58 x 10-5
5.17 x 10-5
3.80 x 10-5

6.09
5.73
5.29
5.00

After
calculating
for
concentrations of [HMR] and [MR-], we
now solve for the value of pKa using
Henderson-Hasselbach equation and
plotting the log[MR-] / [HMR] vs pH.

0.5

1.5

log (MR- / HMR)

Figure 2.1 log [MR-]/ [HMR] vs pH

The pKa value of the system is
graphically shown as the y-intercept. Our
calculated value for pKa is 4.854 and our Ka
value is 1.4 x 10-5. This results in a 2.92%
deviation from the literature value of the pKa
which is 5.00.
A possible error that may have an
effect on the calculated values is the improper
handling of the UV-Vis spectrophotometer.
Improper handling can cause an increase or
decrease in the measured absorbance.

Table 3.1 Conc. of Unknown Samples

[MR-]

A hmr = 25221bchmr + 747.1bcmrA mr- = 3269 bchmr + 9061bcmr-

[HMR]

y = 1.016x + 4.854

After getting the molar absorptivities,

we can now use them to calculate the
unknown concentrations of HMR and MR- in
solutions 7-10. We can calculate them by
using two equations of beer's law.

No.

25221
3269
747.1
9061

hmr
mr hmr
mr-

Table 2.2 Calculated Absorptivities

Solution
Wavelength Absorptivity
HMR

pH

We can calculate for the molar

absorptivities of the two species in two
wavelengths by getting the best fit line and
then getting their slopes.

CONCLUSION AND RECOMMENDATION

the
can
the
by

The calculated pKa had a 2.92% erorr

deviation from the literature value. We can
conclude that the experiment was successful
in obtaining the dissociation constant of
methyl red.
REFERENCES
[1] Purcell, K. F., Kotz, J. C. Organic Chemistry.
W.B. Saunders Company, Philadelphia. 1977.
[2] Cotton, F.A., Wilkinson, G., Murillo, C.A.,
Bochmann, M. Advanced Inorganic Chemistry
6th ed.John Wiley and Sons Inc., Toronto.
1999.
[3] Stafford, F.E., J. Chem Educ.1962, 39, 626.
3

APPENDIX
Ahmr = hmr, hmrbchmr + hmr-, hmrbcmrAmr- = hmr, mr-bchmr + mr-, mr-bcmr-