EXPERIMENT 1: SPECTROPHOTOMETRIC DETERMINATION OF AN ACID DISSOCIATION CONSTANT

2018379186 SINDISWA MINENHLE MNGADI

INTRODUCTION

A technique called spectrophotometry uses light intensity measurements as a beam of light travels
through a sample solution to determine how much a chemical compound absorbs light. The
fundamental idea is that each substance has a specific range of wavelengths within which it either
absorbs or transmits light. The amount of a known chemical compound can also be determined
using this method. [1]

Water acts as a joining forces ligand or reactant in metal complexes, which greatly raises the acidic
concentration of the molecule. This is a result of electron pair attraction to the metal complex. the
water breaking. Strong O-H interactions and significantly stronger H+ ions created by molecules lead
to a medium with a little extra acidity.

Simple weak acids (or bases) that display different colors depending on whether they occur in
solution as their acidic form (HIn) or as their basic form (In-) are known as acid-base indicators. The
equilibrium depicted below will be pushed either towards reactants (HIn) or products (In-) as the pH
of a solution containing the indicator changes, causing the solution color to change depending on
the concentration of each form present. [2]

HIn = H⁺ + In⁻ [1]

The acid dissociation constant (Ka) for the indicator quantitatively describes the relationship
between pH and the relative concentrations of HIn and In- in solution, as indicated in Equation 2,
where the square-bracketed terms reflect the molar concentrations of each species in solution (M).
[2]

Ka = ¿ ¿ [2]

The equilibrium constant of the dissociation reaction of an acid is called the acid dissociation
constant (pka values), and it is provided by Ka. It is a way to quantify how strong an acid is in a
solution. The underlying thermodynamics of the dissociation reaction directly affects the acid
dissociation constant. The reaction's standard Gibbs free energy is directly proportional to the pKa
value, which varies with temperature. Le Chatelier's principle states that when a reaction is
endothermic, the Ka value rises and the pKa falls as the temperature rises. The acid dissociation
constant is essential to comprehending many basic chemical processes. It reveals a molecule's
deprotonation status in a specific solvent.

pKa = -log[Ka]

Derivation of Observed Absorbance from basic principles:

HIn(aq) ↔ In(aq) + H⁺

Ka = ¿ ¿

Aobs = AHIn + AIn⁻

The ratio between the concentration in the acid dissociation equilibrium is:

¿¿
Multiply the acid dissociation constant (Ka) equation: ¿ ¿

Therefore:
Ka
¿¿
Rearranging: Aobs= AHIn ¿¿

The aim of this study is to observe the acid dissociation of an indicator and understand the principles
of acid dissociation of metal complexes and acid indicators.

EXPERIMENT PROCEDURE

0.01M citric acid (0.21014g, 0.001mol) and 0.03M NaOH (0.1200g, 0.003mol) were prepared in 2 ×
100ml beaker, and 0.1012g was dissolved in 20ml of ethanol and diluted with distilled water to the
mark of the volumetric flask (100ml).

5ml of the prepared indicator was pipetted in a 250ml volumetric flask, 50ml of citric acid was added
to the 250ml volumetric flask and diluted to the maker. 100ml of the solution was pipetted into a
250ml beaker and stirred for 10 min until the pH was stabilized. NaOh in increments of 1-0.5ml was
added to the stable solution using a burette until the pH range was 3.4-4.5, and the pH and A obs were
measured. The increment was decreased to 0.1-0.3ml.

435λ was the wavelength used to determine the absorbance of the solution from the
spectrophotometer, firstly the spectrophotometry was calibrated with a blank solution and then
followed by the solution with no sodium hydroxide, and lastly, the solutions with sodium hydroxide
were observed.

All the results were recorded, tabulated and graphed for Ka and std to be calculated.

RESULTS AND DISCUSSION

Tabulated results of pH, absorbance and corrected absorbance after the addition of NaOH to the
solution.

PH ABSORBANCE CORRECTED ABSORBANCE

4,81 0,415 0,416
4,54 0,402 0,406
4,56 0,398 0,396
4,11 0,405 0,406
4,48 0,413 0,416
4,05 0,416 0,416
4,1 0,419 0,416
4,26 0,41 0,416
4,5 0,402 0,406
4,34 0,396 0,396
4,25 0,388 0,386
4,41 0,381 0,386
4,92 0,374 0,376
5,05 0,369 0,366
5,15 0,362 0,366
5,17 0,355 0,356
 5,27 0,351 0,356
5,46 0,346 0,346
5,68 0,342 0,346
5,81 0,339 0,336
Table 1: Show the result of pH, absorbance and corrected absorbance.

The sodium hydroxide was added into the pH stabilized solution in the increment of 1-0.3ml and 20
readings were recorded.

Graph

The graph below represents the pH and absorbance where the solid line is for correct absorbance
and the dots represent the absorbance. The estimated value and standard deviation were obtained,
and the dissociation constant was calculated.

Parameter Name : PKA

Estimate Value = 5.08566327
Standard Deviation = 0.0242145126

pKa= -log[Ka]

Ka= 10−pKa

Ka= 10−5 . 08566327

Ka= 0.0000082099

Graph showing pH versus absorbance

0.42

0.40
Absorbance (Abs)

0.38

0.36

0.34

0.32
4.0 4.5 5.0 5.5 6.0

pH
Graph 1: Absorbance vs pH
In this study, we used bromophenol blue indicator at a less dissociation medium[6]. Beer’s law
provides a direct relationship between light absorbance and analyte concentration (A=Ꜫbc)[4].
Therefore, an increase in NaOH concentration in a solution coursed a decrease in absorbance
because sodium hydroxide is basic making the solution less acidic [3]. The graph does prove that the
less acidic the solution is the will be a decrease in absorbance of the solution. The graph started at a
peak and decreased as the pH increases.

Because of different distribution of ligands in complexes Ka of Rh will differ. The Rh is a weak acid
due to being an inorganic acid, therefore it will have a greater pKa value. How much H⁺ have
dissociated depends on the complexes' charge. Five H⁺ have dissociated from RhTPPS(OH)⁵ˉ
therefore, have lower pKa compared to other Rh complexes.[5]

CONCLUSION

The absorbance decreased as the pH of the solution increases. An increase in pH is due to an

increase in a strong base which is sodium hydroxide. The calculated absorbance and the observed
absorbance are more of the same resulting to have a linear relationship.

REFENCE

[1]. Vo, K. (2022). Spectrophotometry. [online] Chemistry LibreTexts.

Available at:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemis
try_Textbook_Maps/
Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Kinetics/
02%3A_Reaction_Rates/
2.01%3A_Experimental_Determination_of_Kinetics/
2.1.05%3A_Spectrophotometry.

[2]. https://www.facebook.com/thoughtcodotcom (2019). Understand

the Relationship Between pH and pKa. [online] ThoughtCo. Available at:
https://www.thoughtco.com/the-ph-and-pka-relationship-603643.

[3]. www.vedantu.com. (n.d.). Sodium hydroxide is classified as a strong

base $ (NaOH) $ . For every mole of sodium hydroxide added to a large
volume of water. One mole of what ion enters in solution? [online]
Available at: https://www.vedantu.com/question-answer/sodium-
hydroxide-is-classified-as-a-strong-base-class-11-chemistry-cbse-
60dc5ab7b0c53c67f0a4a587 [Accessed 15 Aug. 2023].
[4]. ‌spie.org. (n.d.). Beer’s Law. [online] Available at:
https://spie.org/publications/fg08_p65_beers_law?SSO=1#:~:text=Beer.
[5]. www.google.com. (n.d.). pka of rhtpps(oh)%5E-5 compared to pka of
other rh complexes - Google Search. [online] Available at:
https://www.google.com/search?q=pka+of+rhtpps(oh)%5E-
5+compared+to+pka+of+other+rh+complexes&rlz=1C1GCEB_enZA1071&o
q=&aqs=chrome.6.69i59i450l7j0i3i66i143i362.947065j0j7&sourceid=chrom
e&ie=UTF-8 [Accessed 15 Aug. 2023].

[6]. Socratic.org. (n.d.). Bromophenol blue is an indicator with a

K_a=5.84xx10^(-5). What is the % of indicator in it’s basic form at a
pH=4.84? Given, log(5.84)=0.7664 & antilog of 0.6064 is 4.04. Thank you:) |
Socratic. [online] Available at: https://socratic.org/questions/bromophenol-
blue-is-an-indicator-with-a-k-a-5-84xx10-5-what-is-the-of-indicator-
#:~:text=Explanation%3A [Accessed 15 Aug. 2023].