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EXPERIMENT 8

DETERMINATION OF ACID DISSOCIATION CONSTANT FOR METHYL RED


Name : Chung Kah Yung
Matric No: SEP 050032
Partners Name: Yap Li Fang
Date of experiment: 7 October 2008

INTRODUCTION
The objective of this experiment is to determine the acid dissociation constant for methyl
red which is a type of dye using visible spectrophotometry.
Red methyl present as weak acid. In aqueous solution, red methyl is able to undergo
colour change from reddish to yellowish when we increase the pH value.
HMR H+ + MRK = [H+] [MR-]
[HMR]
In acidic solution it has a bright red color (HMR form) which changes to yellow in its
basic form (MR-). Since the two forms of MR absorb strongly in the visible range, the ratio
[MR-] / [HMR] may be determined spectroscopically.

The concentration of proton, H+ (or H3O+) in the aqueous solution, will determine the
ratio of MR- to HMR, as shown as follows:
[MR-]

[HMR]

[ka]__
[H3O+]

Beer-Lambert Law stated that for any material that absorbs light,
Aobs = Lc
Where

c = concentration
= coefficient of absorption
L = path length

EXPERIMENTAL
1. 100 ml methyl red standard solution is prepared by adding 40 ml of stock solution with 30 ml
of ethanol and diluted with distilled water.
2. Acidic methyl red solution is prepared by adding 5 ml of methyl red stock solution with 10
ml of 0.1 mol dm-3 hydrochloric acid.
3. Basic methyl red solution is prepared by adding 5 ml of methyl red stock solution with 25 ml
of 0.04 mol dm-3 sodium acetate solutions.
4. The spectrums of both solutions are recorded from 400 nm to 700 nm. Wavelengths of
maximum absorbance, A and B for both solutions are chosen. A rough plot is drawn to
obtain the maximum absorbance wavelength.
5. Several red methyl solutions which contain 0.01 mol dm -3 sodium acetate and acetic acid
with concentrations varying 0.001 mol dm-3 to 0.05 mol dm-3 are prepared. Each solution
contained 5 ml of standard red methyl solution. (The total methyl red solution that used for
each solution is the same for those prepared for the acidic and basic solution.)
6. Absorbances of the several solutions are measured at A and B and pH values of each
solution are measured. At least two readings are taken for each measurement.
7. The pH meter must be calibrated with two standard buffer solutions for pH 4 and pH 7.

RESULTS
Concentration of hydrochloric acid = 0.10 mol dm-3
Concentration of sodium acetate solution used = 0.04 mol dm-3

Table 1: Absorption of the acidic methyl red solution from 400 nm to 700 nm

Wavelength, / nm

Absorption, A

400

0.034

425

0.045

450

0.179

475

0.393

500

0.677

525

0.782

521

0.781

550

0.652

575

0.231

600

0.021

625

0.001

650

0.000

675

0.000

700

0.000

Graph 1: Graph of Absorption, A vs Wavelength, /nm for Acidic Methyl Red Solution

From Graph 1, the maximum for acidic methyl red solution, A = 521 nm

Table 2: Absorption of the basic methyl red solution from 400 nm to 700 nm

Wavelength, / nm

Absorption, A

400

0.302

421

0.325

422

0.327

425

0.325

450

0.312

475

0.222

500

0.092

525

0.025

550

0.011

575

0.005

600

0.004

625

0.002

650

0.000

675

0.000

700

0.000

Graph 2: Graph of Absorption, A vs Wavelength, /nm for Basic Methyl Red Solution

From Graph 2, the maximum for basic methyl red solution, B = 422 nm

Table 3: The volume of CH3COONa and CH3COOH required for the preparation of several
methyl red solutions

Concentration of
CH3COOH
(mol dm-3)
0.01
0.01
0.01
0.01

Volume of
CH3COOH
(ml)
25
25
25
25

Concentration of
CH3COONa
(mol dm-3)
0.001
0.005
0.010
0.015

Volume of
CH3COONa
(ml)
1
5
10
15

0.01
0.01
0.01
0.01
0.01
0.01
0.01

25
25
25
25
25
25
25

0.020
0.025
0.030
0.035
0.040
0.045
0.050

20
25
30
35
40
45
50

Table 4: Absorption and pH value for the methyl red solutions with different concentration
of acetic acid
Concentration
of

Absor
ption, Aobs

pH

A =
521 nm

acetic acid,

Tem

B =
422 nm

M/ mol dm-3

Avg

Avg

0.001

0.537

0.533

0.535

0.154

0.156

0.155

4.64 4.63 4.64

0.005

0.578

0.571

0.575

0.135

0.132

0.134

4.51 4.51 4.51

0.010

0.591

0.590

0.591

0.127

0.127

0.127

4.46 4.46 4.46

0.015

0.613

0.612

0.613

0.124

0.119

0.122

4.41 4.41 4.41

0.020

0.625

0.624

0.625

0.115

0.112

0.114

4.34 4.34 4.34

0.025

0.654

0.651

0.653

0.107

0.108

0.108

4.26 4.26 4.26

0.030

0.681

0.681

0.681

0.097

0.098

0.098

4.16 4.16 4.16

0.035

0.714

0.709

0.712

0.096

0.098

0.097

4.02 4.02 4.02

0.040

0.733

0.733

0.733

0.079

0.084

0.082

3.79 3.80 3.80

0.045

0.757

0.762

0.760

0.074

0.071

0.073

3.44 3.47 3.46

0.050

0.770

0.768

0.769

0.063

0.063

0.063

3.09 3.12 3.11

Table 5: Value of [H+], Aobs - AobsA and 1/ ( Aobs - AobsA) at A = 521 nm where AobsA = 0.781

Avg

pH

[H+] x 10-5

Aobs - AobsA

1/( Aobs - AobsA)

(mol dm-3)
4.64

2.2909

-0.246

-4.0650

4.51

3.0903

-0.206

-4.8544

4.46

3.4674

-0.190

-5.2632

4.41

3.8905

-0.168

-5.9524

4.34

4.5709

-0.156

-6.4103

4.26

5.4954

-0.128

-7.8125

4.16

6.9183

-0.100

-10.0000

4.02

9.5499

-0.069

-14.4928

3.80

15.8489

-0.048

-20.8333

3.46

34.6737

-0.021

-47.6190

3.11

77.6247

-0.012

-83.3333

Graph 3: Graph of 1/ (Aobs - AobsA) vs [H+] at A = 521 nm

Table 6: Value of [H+], 1/ [H+], Aobs - AobsB and 1/ ( Aobs - AobsB) at B = 422nm where AobsB =
0.327
[H+]

1/ [H+]

x 10-5

x105 (dm3 mol-1)

Aobs - AobsB

1/( Aobs - AobsB)

(mol dm-3)
2.2909

0.4365

-0.172

-5.8140

3.0903

0.3236

-0.193

-5.1813

3.4674

0.2884

-0.200

-5.0000

3.8905

0.2570

-0.205

-4.8780

4.5709

0.2188

-0.213

-4.6948

5.4954

0.1820

-0.219

-4.5662

6.9183

0.1445

-0.229

-4.3668

9.5499

0.1047

-0.230

-4.3478

15.8489

0.0631

-0.245

-4.0816

34.6737

0.0288

-0.254

-3.9370

77.6247

0.0129

-0.264

Graph 4: Graph of 1/ (Aobs - AobsB) vs 1/ [H+] at B = 422 nm

CALCULATIONS
1. KA value

From Graph 3,
y-intercept, c = -2.6708
uncertainty of y-intercept, c = 1.0735
gradient, m = -1.0826 x 105 mol-1dm3
uncertainty of gradient, m = 0.0405 x 105 mol-1dm3

KA

= y-intercept / gradient

-3.7879

= -2.6708 / (-1.0826 x 105) mol-1dm3


= 2.4670 x 10-5 mol dm-3

KA= (m/m + c/c) x KA


= [(0.0405 x 105 / -1.0826 x 105) + (1.0735 / -2.6708)] x 2.4670 x 10-5 mol dm-3
= -1.0839 x 10-5 mol dm-3

Thus, KA = (2.4607 1.08) x 10-5 mol dm-3

2. KB value

From Graph 4,
y-intercept, c = -3.7697
uncertainty of y-intercept, c = 0.0343
gradient, m = -4.4597 x 10-5 mol dm-3
uncertainty of gradient, m = 0.1515 x 10-5 mol dm-3

KB

= gradient / y-intercept
= -4.4597 x 10-5 mol dm-3 / -3. 7697
= 1.1830 x 10-5 mol dm-3

KB= (m/m + c/c) x KB


= [(0.1515 x 10-5 / -4.4597 x 10-5) + (0.0343 / -3.7697)] x 1.1830 x 10-5 moldm-3
= -5.0952 x 10-7 mol dm-3

Thus, KB = (1.1830 0.0510) x 10-5 mol dm-3

DISCUSSIONS
At the beginning of this experiment, we determine the highest absorption of both acidic
and basic methyl red solutions in order to obtain the suitable wavelength for the determination of
acid dissociation constant for methyl red. The takings of absorptions are narrowed down to the
more precise wavelength to get the highest absorption. So, the wavelength suitable in acidic
methyl red solution is 521nm whereas for the basic solution is 422 nm.

From the preparation of several methyl red solutions with different acetic acid
concentration, we can observe that there is a trend in the colour changes. The colour of the
solution tends to be more reddish when the concentration of acetic acid is high, low pH and it
tends to be yellowish when the concentration is decreasing, increasing in pH, increasing basicity.
While the concentration of hydrogen ions is not only come from the dissociation of acetic acid
but also from the dissociation of methyl red solution. This can be observed through the results
obtained in the experiment.

HMR

H+

MR-

For acidic methyl red solution, A = 521 nm is applied in determining absorption. The
absorption is directly proportional to the concentration of the acetic acid. The higher the
concentration of acetic acid, the higher the absorption is it. According to the Le Chateliers
Principle, the equivalence system tends to go left hand side because of the higher concentration
of H+. The HMR species is the dominant comparing to MR-.

Absorptions obtained are below the maximum absorption of acidic solution due to the
lower concentration of H+ ions between acetic acid, CH3COOH and hydrochloric acid, HCl.
Acetic acid dissociates partially and not 100% dissociated as HCl. This means that acetic acid
was affected by common ion effect from CH3COONa. It dissociates almost 100% to produce

CH3COO- anions similar to acetic acid. Ionization of acetic acid was pushed by CH 3COO- anions.
The mixture of solutions produces a buffer solution that will control the pH changes respected
to the acidity or basicity changes of the solution.

For the basic methyl red solution, B = 422 nm is applied. The absorptions are inversely
proportional to the concentration of acetic acid. The higher the concentration of acetic acid, the
lower the absorption is it. The system tends to move towards right hand side when there is lower
acetic acid concentration. At this point, the ratio of sodium acetate is much higher compare to
acetic acid.

We notice that the acid dissociation constant of methyl red is higher than the literature
value (3.8 x 10-6 mol dm-3). This is because of the experimental temperature (T = 30C) which is
higher than the standard room temperature. Higher temperature encourages the ionization of red
methyl.

CONCLUSION
Acid dissociation constant for methyl red is:
a. KA = (2.4607 1.08) x 10-5 mol dm-3
b. KB = (1.1830 0.0510) x 10-5 mol dm-3

REFERENCES
1. Peter Atkins & Julio de Paula. Atkins Physical Chemistry (7th edition), Oxford

University Press, pp. 491.


2. Laboratory Manual, Year III, Department of Chemistry, University of Malaya,
Session 08/09, pp. 51-56.

ANSWERS TO QUESTIONS

ci L
Aobs A B obs

K
1

[ H ] A B ( A B )

. (1)

A B obs B ci L .. (2)
1. Derive equation (1) starting from (2).
In basic red methyl solution,

A B obs B ci L .. (2)
Where, ci is concentration,
L is path length,
is the coefficient of absorption.
From Beer Lambert law,
Aobs b ci L

..........................................

(3)

(3) (2) will yield

ci L
1

............. (4)
b B Aobs A B obs
Let A = HMR and B = MR-,
Then,

H B ........ (5)

The absorbance, Aobs for a particular wavelength is given by,


Aobs A A B B L ........ (6)

Equation (6) also can be written as Aobs a A B L ........ (7)


From equation (6) and (7),

A B a
B a A ....... (8)
When substitute (8) into (5),

B a ( B A ) ( a A
a A =
a A

K
H

A B
b B
Multiply equation (9) with

( A B ) ( b B )
b B

K
H

....... (9)

1
,
A B

1
K
1
1


..... (10)

b B [H ] A B A B

From equation (4) and (10),

ci L
Aobs A B obs

K
1

[ H ] A B ( A B )

2. Compare K values obtained from


A

obs

a ci L

. (1) and

A A obs A ci L ... (2)


Which of these values are accurate.
The K value obtain from both equation are different. From the calculation of (1),
K value obtained is (2.4607 1.08) x 10-5 mol dm-3 while the calculation of (2) give the value of
(1.1830 0.0510) x 10-5 mol dm-3. This is due to the graph that plotted. The sharper for the graph
peak will give a more accurate value of acid dissociation constant, K. From the results obtained,

peak for graph 1 (A = 521 nm) is sharper than graph 2 ( B = 422 nm), therefore the K value
which is more accurate should be the K value from A = 521 nm, which is (2.4607 1.08) x 10-5
mol dm-3.

3. Discuss whether the experiment can be performed using wavelengths other than A
and B.
The experiment cannot be performed using wavelengths other than A and B. This is
because both of the wavelengths are the most suitable wavelength to be used in these
measurements since they are the maximum absorption wavelength obtained by the acidic and
basic methyl red solution. By using A and B, the absorption obtained will be more accurate.