EXPT 2.

SEPARATION OF MALACHITE GREEN AND PHENOLPHTHALEIN

(ACID-BASE EXTRACTION)
Bea Lorraine S. Acosta and Izza May L. Tomas
Locker No. 82

Chemistry Department, Xavier University - Ateneo de Cagayan, Cagayan de Oro City

Date Performed: July 3, 7, 2017
Date Submitted: July 10, 2017

ABSTRACT

Malachite green and phenolphthalein are two dyes that are used as pH indicators. Malachite
green is blue-green in color in acidic environment, while phenolphthalein is dark pink in basic
environment. Acid-base extraction is liquid-liquid extraction that involves different solubility levels in
water and an organic solvent. Acid-base extraction was used to separate and isolate malachite green
and phenolphthalein. The isolated malachite green was blue-green in color. The phenolphthalein was
purified with hot ethanol; it was green in color instead of colorless. The melting point of the purified
phenolphthalein was 264.4C, with an error of 1.69%.

INTRODUCTION

Extraction involves dissolving a compound or compounds either (1) from a solid into a solvent or
(2) from a solution into another solvent (1). The purpose of this experiment was to separate malachite
green and phenolphthalein by acid-base extraction. For the process to be selective, the compound must
be more soluble in the second solvent than in the first solvent, and the impurities must be insoluble in
the second solvent. Additionally, the two selected solvents must be immiscible, or not soluble in one
another, so that they produce two separate solvent layers (2). After dissolving the mixture in the first
solvent, the solution is added to a second solvent. The two layers are vigorously mixed to maximize the
surface area between them. This mixing facilitates the transfer of a dissolved compound from one
solvent layer to another. Once the transfer process is complete, the layers are again allowed to form,
separation of the two layers then completes the separation of the desired compound from the
impurities.
A liquid-liquid extraction is an important separation technique. In a simple liquidliquid
extraction the solute partitions between two immiscible phases. One phase usually is aqueous and the
other phase is an organic solvent. Because the phases are immiscible they form two layers, with the
denser phase on the bottom. The solute is initially present in one of the two phases; after the extraction
it is present in both phases. A type of liquid-liquid extraction is acid-base extraction. (2)
An acid-base extraction is a type of liquid-liquid extraction; it involves different solubility levels
in water and an organic solvent. The organic solvent may be any carbon-based liqiuid that does not
dissolve very well in water; common ones are ether, ethyl acetate, or dichloromethane. Acid-base
extraction is used to separate organic compounds from each other based on their acid-base
properties. The method rests on the assumption that most organic compounds are more soluble in
organic solvents than they are in water. However, if the organic compound is rendered ionic, it
becomes more soluble in water than in the organic solvent. These compounds can easily be made into
ions either by adding a proton (an H+ ion), making the compound into a positive ion, or by removing a
proton, making the compound into a negative ion. In this experiment, acid-base extraction is employed
to isolate malachite green and phenolphthalein. (3)
Malachite green is an organic compound that is used as a dyestuff and controversially as an
antimicrobial in aquaculture. Malachite green is traditionally used as a dye for materials such as silk,
leather, and paper. Malachite green is classified in the dyestuff industry as a triarylmethane dye and also
using in pigment industry. Formally, malachite green refers to the chloride salt [C6H5C(C6H4N(CH3)2)2]Cl,
although the term malachite green is used loosely and often just refers to the colored cation. The
intense green color of the cation results from a strong absorption band at 621 nm. (4)(Wikipedia, May
13, 2017)
Phenolphthalein is an organic compound of the phthalein family that is widely employed as an
acid-base indicator. As a pH indicator, phenolphthalein is colorless below pH 8.5 and attains a pink to
deep red hue above pH 9.0. Phenolphthalein, which is closely related to the triphenylmethane dyes, was
discovered in 1871 by the German chemist Adolf von Baeyer, who prepared it by fusing phenol and
phthalic anhydride in the presence of sulfuric acid or zinc chloride, the procedure still employed.(5)

MATERIALS AND METHOD

In the separation of malachite green and phenolphthalein by acid-base titration, 0.15 g of

phenolphthalein and 0.1 g of malachite green were added to 15-ml 3M NaOH in a separatory funnel and
the mixed; 10-ml of diethyl ether was then added and mixed thoroughly. The aqueous layer was drained
off through the stopcock and the ether layer was decanted into a flask. The aqueous layer was returned
to the separatory funnel, and then washed with two more 10-ml portions of ether; all ether layers
extracted were combined.
In the isolation of Malachite green oxalate, a mixture of 0.08g of oxalic acid and 5-ml of ether
was added to the ether extract. The mixture was set aside for 10 minutes and placed in an ice bath for
another 10 minutes. The product was collected via suction filtration and washed with ether.
In the isolation of phenolphthalein, if solid was present, the aqueous layer was filtered by
gravity. Any remaining ether mixture was removed with pipet. The aqueous layer was then acidified
with about 7.5-ml 6M HCl. The mixture was allowed to stand for 10 minutes and then placed in an ice
bath for another 10 minutes. The mixture was then filtered by suction filtration and washed with water.
In the purification of phenolphthalein, the solid was dissolved in 1.5-ml hot ethanol and then 5-ml water
was added with heating. The mixture was then crystalized through cooling and collected by suction
filtration. The melting point of the purified phenolphthalein was determined via the melting point
analyzer.
RESULTS AND DISCCUSION

Acid-base extraction is a type of liquid-liquid extraction; it involves different solubility levels in

water and an organic solvent. Acid-base extraction is used to separate organic compounds from each
other based on their acid-base properties. In this experiment the acid-base properties utilized in the
separation of malachite green and phenolphthalein is their color since both compounds are used as pH
indicators.

Figure 1. Phenolphthalein and malachite green structures at acidic and basic environment.

Upon addition of the dye mixture to NaOH, the solution immediately turned dark pink due to
the phenolphthalein, which turns to a dark pink color in basic conditions. When the ether layer was
added, malachite green was dissolved and the layer turned to a blue-green color; after mixing the color
became yellow. Malachite green was in the organic layer while phenolphthalein was in the aqueous
layer. Since NaOH is much denser than ether, the aqueous layer was the bottom layer and the organic
layer the top layer. The layers were then separated followed by the isolation of malachite green and
phenolphthalein.
 (a) (b)
Figure 2. (a) Aqeuos phase and (b) organic phase.

In the isolation of malachite green, the solution was acidified with oxalic acid, turning the
solution into a blue-green color since the compound is blue-green in color at acidic conditions. The
malachite green was then crystallized via ice bath.

(a) (b)
Figure 3. Precipitated (a) malachite green and (b) phenolphthalein.

In the isolation of phenolphthalein, the remaining solids were removed and the solution was
acidified with HCl; in acidic environment phenolphthalein is colorless. After acidification the solution
turned white, and green precipitate formed; it was placed in an ice bath to further crystallize the
phenolphthalein. The collected solids were purified by the addition of hot ethanol and washing with
water, and then crystallized again in an ice bath. The purified phenolphthalein was green in color; its
melting point was determined to be 264.4C; the MPlit of phenolphthalein was 260C. The percent error
was calculated to be 1.69.
Error Analysis

The purified phenolphthalein was supposed to be colorless solid, but instead it was green in
color. This is probably due to the undissolved malachite green that was removed with the aqueous
phase and some of the malachite green dissolved in the aqueous phase instead; and/or due to
incomplete purification of the phenolphthalein.

CONCLUSION

In this experiment, acid-base extraction was used to separate and isolate malachite green and
phenolphthalein; and the melting point of purified phenolphthalein was determined. The isolated
malachite green was blue-green in color. The phenolphthalein was purified with hot ethanol; it was
green in color instead of colorless. The melting point of the purified phenolphthalein was 264.4C, with
an error of 1.69%.

REFERENCES

(1) Chemistry LibreTexts. (2016). 7.6: Classifying Separation Techniques. [online] Available at:
https://chem.libretexts.org/Textbook_Maps/Analytical_Chemistry_Textbook_Maps/Map%3A_Analytical
_Chemistry_2.0_(Harvey)/07%3A_Collecting_and_Preparing_Samples/7.6%3A_Classifying_Separation_T
echniques [Accessed 9 Jul. 2017].

(2) Chemistry LibreTexts. (2016). 7.7: LiquidLiquid Extractions. [online] Available at:
https://chem.libretexts.org/Textbook_Maps/Analytical_Chemistry_Textbook_Maps/Map%3A_Analytical
_Chemistry_2.0_(Harvey)/07%3A_Collecting_and_Preparing_Samples/7.7%3A_Liquid%E2%80%93Liquid
_Extractions [Accessed 9 Jul. 2017].

(3) Chemistry LibreTexts. (2016). Acid-Base Extraction. [online] Available at:

https://chem.libretexts.org/Core/Analytical_Chemistry/Lab_Techniques/Acid-Base_Extraction [Accessed
9 Jul. 2017].

(4) En.wikipedia.org. (2017). Malachite green. [online] Available at:

https://en.wikipedia.org/wiki/Malachite_green [Accessed 9 Jul. 2017].

(5) Encyclopedia Britannica. (2001). phenolphthalein | chemical compound. [online] Available at:
https://www.britannica.com/science/phenolphthalein [Accessed 9 Jul. 2017].
Answers to Questions:
1. Calculate the pH of each aqueous solution in this experiment.
a. 30 mL 3M NaOH

b. aqueous layer after 16 mL 6M HCl was added.

2. a. A student proposed to separate the mixture using 20mL 3M HCl and ether in the first step
instead of NaOH. How would this change the separation? What would be in each layer?

b. Assuming that the student was successful above, what would the second step be to complete
the separation? (Hint: what pH would the student need to obtain?)
Calculation:

|264.4 260|
% = 100 = .
260