166 5 SIMPLE MIXTURES

Mixtures for which the solute obeys Henry’s law and the solvent obeys Raoult’s law
are called ideal-dilute solutions. We shall also label equations with a superscript °
when they have been derived from Henry’s law. The difference in behaviour of the
solute and solvent at low concentrations (as expressed by Henry’s and Raoult’s laws,
respectively) arises from the fact that in a dilute solution the solvent molecules are in
an environment very much like the one they have in the pure liquid (Fig. 5.15). In
contrast, the solute molecules are surrounded by solvent molecules, which is entirely
different from their environment when pure. Thus, the solvent behaves like a slightly
modified pure liquid, but the solute behaves entirely differently from its pure state
unless the solvent and solute molecules happen to be very similar. In the latter case,
the solute also obeys Raoult’s law.
Fig. 5.15 In a dilute solution, the solvent
molecules (the blue spheres) are in an
Example 5.3 Investigating the validity of Raoult’s and Henry’s laws
environment that differs only slightly from
that of the pure solvent. The solute The vapour pressures of each component in a mixture of propanone (acetone, A)
particles, however, are in an environment and trichloromethane (chloroform, C) were measured at 35°C with the following
totally unlike that of the pure solute. results:
50 xC 0 0.20 0.40 0.60 0.80 1
p*(acetone) pC /kPa 0 4.7 11 18.9 26.7 36.4
pA/kPa 46.3 33.3 23.3 12.3 4.9 0
40
p*(chloroform) Confirm that the mixture conforms to Raoult’s law for the component in large ex-
cess and to Henry’s law for the minor component. Find the Henry’s law constants.
Pressure, p/kPa

Raoult’s
30 law
Method Both Raoult’s and Henry’s laws are statements about the form of the
K(acetone)
K(chloroform) graph of partial vapour pressure against mole fraction. Therefore, plot the partial
20 vapour pressures against mole fraction. Raoult’s law is tested by comparing the
data with the straight line pJ = xJ p *J for each component in the region in which it is
in excess (and acting as the solvent). Henry’s law is tested by finding a straight line
10
pJ = xJ K *J that is tangent to each partial vapour pressure at low x, where the com-
Henry’s
law
ponent can be treated as the solute.
0
0 1 Answer The data are plotted in Fig. 5.16 together with the Raoult’s law lines.
Mole fraction of
chloroform, x(CHCl3) Henry’s law requires K = 23.3 kPa for propanone and K = 22.0 kPa for
trichloromethane. Notice how the system deviates from both Raoult’s and Henry’s
Fig. 5.16 The experimental partial vapour
laws even for quite small departures from x = 1 and x = 0, respectively. We deal with
pressures of a mixture of chloroform
these deviations in Sections 5.10 and 5.11.
(trichloromethane) and acetone
(propanone) based on the data in Example
5.3. The values of K are obtained by Self-test 5.4 The vapour pressure of chloromethane at various mole fractions in a
extrapolating the dilute solution vapour mixture at 25°C was found to be as follows:
pressures as explained in the Example.
x 0.005 0.009 0.019 0.024
p/kPa 27.3 48.4 101 126
Table 5.1* Henry’s law constants for
gases in water at 298 K Estimate Henry’s law constant. [5 MPa]
K /(kPa kg mol−1)
For practical applications, Henry’s law is expressed in terms of the molality, b, of
CO2 3.01 × 103
the solute, pB = bB KB. Some Henry’s law data for this convention are listed in Table 5.1.
H2 1.28 × 105
As well as providing a link between the mole fraction of solute and its partial pressure,
N2 1.56 × 105
the data in the table may also be used to calculate gas solubilities. A knowledge of
O2 7.92 × 104
Henry’s law constants for gases in blood and fats is important for the discussion of
respiration, especially when the partial pressure of oxygen is abnormal, as in diving
* More values are given in the Data section.
and mountaineering, and for the discussion of the action of gaseous anaesthetics.
 Christian7e c18.tex V2 - 08/20/2013 8:46 A.M. Page 583

18.4 SOLVENT EXTRACTION OF METALS 583

(a) one extraction with 40 mL of toluene;

(b) two extractions with 20 mL of toluene each;
(c) four extractions with 10 mL of toluene each?

Solution

(a) Fraction remaining = [Va /(DVo + Va )]n =[20/(10 × 40 + 20)]1 = 0.048 = 4.8%;
Extracted approximately 95% of A.
(b) Fraction remaining = [20/(10 × 20 + 20)]2 = 0.0083 = 0.83%
Extracted approximately 99% of A.
(c) Fraction remaining = [20/(20/10 × 20 + 20)]4 = 7.7 × 10−4 = 0.077%
Extracted approximately 100% of A.
Conclusion: Several extractions using small portions of organic solvent allows one to
separate the analyte more efficiently than one large-portion extraction. 

18.4 Solvent Extraction of Metals

Solvent extraction has one of its most important applications in the separation of metal To extract a metal ion into an
cations. In this technique, the metal ion, through appropriate chemistry, distributes from organic solvent, its charge must be
an aqueous phase into a water-immiscible organic phase. Solvent extraction of metal neutralized, and it must be
ions is useful for removing them from an interfering matrix, or for selectively (with associated with an organic agent.
the right chemistry) separating one or a group of metals from others. The technique is
widely used for the spectrophotometric determination of metal ions since the reagents
used to accomplish the extraction often form colored complexes with the metal ion. It
is also used in flame atomic absorption spectrophotometry for introducing the sample
in a nonaqueous solvent into the flame for enhanced sensitivity, and removal of matrix
effects.
The separation can be accomplished in several ways. You have noted above
that the uncharged organic molecules tend to dissolve in the organic layer while the
charged anion from the ionized molecules remains in the polar aqueous layer. This is
an example of “like dissolves like.” Metal ions do not tend to dissolve appreciably in
the organic layer. For them to become soluble, their charge must be neutralized and
something must be added to make them organic-like. There are two principal ways of
doing this.

EXTRACTION OF ION-ASSOCIATION COMPLEXES

In one method, the metal ion is incorporated into a bulky molecule and then associates
with another ion of the opposite charge to form an ion pair, or the metal ion associates
with another ion of great size (organic-like). For example, it is well known that iron(III)
can be quantitatively extracted from hydrochloric acid medium into diethyl ether. The
mechanism is not completely understood, but evidence exists that the chloro complex
of the iron is coordinated with the oxygen atom of the solvent (the solvent displaces the
coordinated water), and this ion associates with a solvent molecule that is coordinated
with a proton:
{(C2 H5 )2 O : H+ , FeCl4 [(C2 H5 )2 O]2 − }
Similarly, the uranyl ion UO2 2+ is extracted from aqueous nitrate solution into
isobutanol by associating with two nitrate ions (UO2 2+ , 2NO3 − ), with the uranium
 Jurnal Forum Nuklir (JFN) Volume 10, Nomor 1, Mei 2016

EKSTRAKSI DAN STRIPPING TORIUM DARI RAFINAT HASIL

EKSTRAKSI URANIUM MONASIT BANGKA
Rida Ferliana 1, Bangun Wasito 1, Riesna Prassanti 2

1) Teknokimia Nuklir STTN-BATAN, Jl. Babarsari, Kotak Pos 6101 YKBB Yogyakarta
55281
2) PTBGN-BATAN, Jl. Lebak Bulus Raya No.9. Ps. Jumat, Jakarta 12440

ABSTRAK

EKSTRAKSI DAN STRIPPING TORIUM DARI RAFINAT HASIL EKSTRAKSI URANIUM MONASIT
BANGKA. Pusat Teknologi Bahan Galian Nuklir–Badan Tenaga Nuklir Nasional (PTBGN-BATAN) yang
bekerja sama dengan PT Timah mengimplementasikan penelitian pengolahan monasit menjadi logam tanah
jarang ke dalam skala pilot plant 50 kg/hari. Kegiatan tersebut menghasilkan limbah berupa unsur radioaktif,
seperti uranium dan torium. Torium merupakan alternatif pengganti bahan bakar uranium. Agar dapat
dijadikan bahan bakar nuklir, torium perlu dipisahkan terlebih dahulu. Salah satu metode pemisahan adalah
ekstraksi-stripping. Ekstraksi-stripping torium dilakukan dengan menggunakan rafinat hasil ekstraksi
uranium pada limbah pengolahan monasit. Solvent yang digunakan dalam ekstraksi adalah TBP dan dalam
stripping adalah HNO3 encer. Berdasarkan penelitian diperoleh bahwa semakin tinggi keasaman umpan,
maka recovery dan koefisien distribusi torium semakin meningkat; serta semakin tinggi konsentrasi HNO3,
maka recovery semakin menurun dan koefisien distribusi torium semakin meningkat. Ekstraksi selama 15
menit, pH umpan 0,09, TBP/kerosen 50/50, dan perbandingan A/O = 1/1 memberikan koefisien distribusi
sebesar 13,80 dengan recovery ekstraksi sebesar 93%. Stripping selama 15 menit, konsentrasi HNO3 0,1 N,
dan perbandingan A/O = 1/1 memberikan koefisien distribusi 1,57 dengan recovery sebesar 38,92%. Jika
recovery torium ingin ditingkatkan menjadi 95%, maka dibutuhkan 2 stage ekstraksi pada perbandingan A/O
= 1/1, 8 stage stripping pada perbandingan A/O = 2/1, dan 5 stage stripping pada perbandingan A/O = 3/1.

Kata kunci: monasit, ekstraksi, stripping, torium, uranium, logam tanah jarang, koefisien distribusi, stage

ABSTRACT

THORIUM EXTRACTION AND STRIPPING FROM URANIUM EXTRACTION RAFFINATE OF BANGKA

MONAZITE. Centre for Nuclear Mineral Geology–National Nuclear Energy Agency in cooperation with PT
Timah (TINS) has conducted a project of turning monazite into rare earth elements pilot plant of 50 kg/day.
This project would produce radioactive wastes such as uranium and thorium. Thorium is an alternative fuel
source to uranium. In order to be able to be used as nuclear fuel, the impurities must be separated from the
thorium. One of the separation methods is extraction-stripping. Extraction and stripping of thorium was
made by using raffinate of uranium extraction of rare earth elements wastes. Solvent used in extraction is
TBP and in stripping is diluted acid. This research showed that the higher the acidity of feed, the more
possibility of recovery and distribution coefficients of thorium will increase in the extraction; and the higher
the concentration of HNO3, the more possibility of recovery will decrease and distribution coefficients of
thorium in the stripping will increase. Extraction in 15 minutes, with feed pH 0,09, TBP/kerosene 50/50, and
A/O = 1/1 resulted in a distribution coefficient of 13,8 with the recovery of thorium to be 93,24%. Stripping
in 15 minutes, with HNO3 0,1 N, and A/O = 1/1 resulted in a distribution coefficient of 1,57 with the recovery
of thorium to be 38,92%. To increase recovery of thorium up to 95%, it would need two stages of extraction
of A/O = 1/1, 8 stages of stripping of A/O = 2/1, and 5 stages of stripping of A/O = 3/1.

Keywords: monazite, extraction, stripping, thorium, uranium, rare earth element, distribution coefficient,
stage

26 Ekstraksi dan Stripping Torium ...

 Jurnal Forum Nuklir (JFN) Volume 10, Nomor 1, Mei 2016
molekul seperti pada Gambar 2. Atom oksigen
pada gugus P=O merupakan basa lewis dan
bertindak sebagai atom donor yang dapat
memberikan pasangan elektron bebas pada
orbital kosong torium, uranium, dan LTJ [9].
Gambar 2. Struktur Tri-butil-fosfat
Stripping Torium
Ekstraksi uranium menggunakan TBP lebih
kuat dibandingkan pada torium dan logam
tanah jarang. Langkah penting dalam
pemisahan uranium dan torium adalah
stripping. Pada proses stripping, torium dapat
diambil dari ekstraksi TBP dengan
menggunakan asam encer, sedangkan uranium
dapat diambil dengan menggunakan air
demineralisasi [6].
Koefisien Distribusi
Dalam ekstraksi maupun stripping, ketika
larutan aqueous dikontakkan dengan solvent
Gambar 3. Ekstraksi Multistage Berlawanan Arah [7]
Jumlah stage yang dibutuhkan dapat
ditentukan dengan cara berikut.
a. Metode Grafik McCabe-Thiele
Persamaan garis operasi dapat ditentukan
dengan membuat neraca massa berdasarkan
Gambar 3.
Neraca massa pada setiap stage dinyatakan
dengan Persamaan (2).
FX F + SYn +1  RX n + EY1 (2)
Karena solvent dan larutan umpan tidak saling
melarutkan maka F = R dan S = E sehingga
Persamaan (2) dapat diubah menjadi:
FX F + SYn +1 = FX n + SY1 (3)
28
yang tidak saling melarutkan, komponen yang
diekstrak akan ditemukan terdistribusi di
antara dua fase, yaitu fase organik dan fase
aqueous. Distribusi ini dapat dinyatakan
dengan koefisien distribusi. Salah satu faktor
penting dalam pemisahan ekstraksi-stripping
adalah koefisien distribusi, yang dinyatakan
dalam Persamaan (1).
[unsur ]organik
Kd  (1)
[unsur ]aqueous
Nilai koefisien distribusi pada ekstraksi
diharapkan tinggi, sedangkan nilai koefisien
distribusi pada stripping diharapkan rendah
[7].
Ekstraksi Multistage dengan Aliran
Berlawanan Arah (Counter Current)
Prinsip ekstraksi multistage counter current
adalah mengontakkan umpan “baru” dengan
solvent yang telah mengandung banyak solute.
Solute tersebut merupakan ekstrak yang
diperoleh sebagai hasil kontak pada stage
berikutnya. Kemudian, umpan dengan solute
yang telah menipis dikontakkan dengan
pelarut pada tahap berikutnya, seperti pada
Gambar 3.
F
Yn 1  ( X n  X F )  Y1 (4)
S
Xn adalah fraksi massa solute dalam rafinat
yang meninggalkan proses; XF adalah fraksi
massa solute dalam umpan yang masuk ke
proses; F adalah kecepatan aliran massa
umpan, S adalah kecepatan aliran massa
solvent, dan Yn+1 = Ys adalah fraksi massa
solute dalam ekstraktan yang masuk ke proses.
Metode McCabe-Thiele juga dapat
diterapkan berdasarkan konsentrasi solute di
dalam ekstrak dan rafinat. Definisi laju alir,
konsentrasi, dan jumlah stage ditunjukkan pada
Gambar 4 dengan mengasumsikan bahwa
kesetimbangan dicapai antara fase aqueous dan
fase organik yang meninggalkan masing-
masing stage.
Ekstraksi dan Stripping Torium ...
 Jurnal Integrasi Proses Vol. 6, No. 4 (Desember 2017) 162 - 167

JURNAL INTEGRASI PROSES

Website: http://jurnal.untirta.ac.id/index.php/jip

Submitted : 15 September 2017 Revised : 27 Oktober 2017 Accepted : 21 November 2017

EKSTRAKSI FLAVONOID DARI BAYAM MERAH (Alternanthera Amoena Voss)

Salwa Jody Gustia1*, Irsa Septiawan, Iriany1

1Departemen Teknik Kimia, FakultasTeknik ,Universitas Sumatera Utara
*Email: gustiasalwa02@gmail.com

Abstrak
Bayam merah (Alternanthera Amoena Voss) mengandung senyawa antioksidan seperti betalain, karatenoid,
vitamin C dan flavonoid. Senyawa antioksidan berfungsi untuk menetralkan radikal bebas didalam tubuh, sehingga
tubuh terlindungi dari penyakit degeneratif. Pengambilan senyawa flavonoid pada bayam merah dilakukan
dengan proses ekstraksi. Penelitian ini bertujuan untuk mendapatkan koefisien perpindahan massa (Kc) pada
proses ekstraksi bayam merah, mengkaji hubungan antara kecepatan pengadukan dengan koefisien perpindahan
massa, serta aktivitas antioksidan dari flavonoid yang diperoleh. Hubungan nilai Kc dengan kecepatan pengadukan
dinyatakan dalam persamaan bilangan tak berdimensi Sherwood (Sh). Bayam merah yang sudah dipotong dengan
ukuran 1 x 1 cm diekstraksi dengan menggunakan pelarut aquadest dalam bejana berpengaduk pada suhu tetap
yaitu 60oC dan kecepatan pengadukan 100 rpm, 200 rpm dan 300 rpm. Setiap 5 menit cuplikan sampel diambil
dan diukur kadar total flavonoidnya dengan menggunakan spektrofotometer UV-VIS. Proses ekstraksi berhenti
ketika telah terjadi kondisi setimbang. Kesimpulan yang diperoleh dari penelitian ini adalah nilai Kc meningkat
seiring dengan meningkatnya kecepatan pengadukan, dan persamaan bilangan tak berdimensi sherwood pada
proses ekstraksi flavonoid dari bayam merah adalah Sh = 240,6154Re 0,6195.

Kata Kunci: antioksidan, bilangan sherwood, koefisien perpindahan massa

Abstract

Red spinach (Alternanthera Amoena Voss) contains antioxidant compounds such as betalain, karatenoid, vitamin C
and flavonoids. Antioxidant compounds serve to neutralize free radicals in the body, so that the body is protected from
degenerative diseases. The separation of flavonoid compounds from red spinach is carried out by using extraction
process. This study aims to obtain mass transfer coefficient (Kc) in red spinach extraction process and study the
relationship between agitation speed with mass transfer coefficient, and antioxidant activity of the flavonoids
obtained. The relationship of Kc and agitation speed is expressed in an equation of Sherwood Number (Sh). Red
spinach that had been cut to the square sized (1 x 1 cm) was extracted by using aquadest in an agitated vessel at a
temperature of 60oC and agitation speed of 100 rpm, 200 rpm and 300 rpm. Every 5 minutes sample was taken and
its total flavonoid was measured using a UV-VIS spectrophotometer at 415 nm. The extraction process terminated
after the equilibrium condition had been reached. The conclusion obtained from this study is the value of Kc increases
along with the increasing of agitation speed and equation of sherwood number (Sh) for this extraction is Sh =
240,6154Re 0,6195.

Keywords: antioxydant, sherwood number, mass transfer coefficient

1. PENDAHULUAN obatan dan tanaman industri (Hardjono dan

Indonesia merupakan salah satu negara yang
sebagian besar penduduknya bertumpu pada bidang
pertanian.Bumi Indonesia yang subur ini mampu
memproduksi beraneka ragam tanaman yang
bermanfaat seperti tanaman pangan, tanaman obat-
Yamrewav, 2004).
Senyawa-senyawa sintetik yang mempunyai
aktivitas antioksidan seperti senyawa antioksidan
sintetik butylated hydroxyl toluen (BHT), butylated
hydroxyanisole (BHA) dan tert-butyl hydroxy quinone
(TBHQ) dibatasi penggunaannya karena bersifat
162
 Jurnal Integrasi Proses Vol. 6, No. 4 (Desember 2017) 162 - 167
karsinogenik (Erawati, 2012). Oleh karena itu, perlu
dilakukan penelitian lebih lanjut untuk menghasilkan
senyawa antioksidan alami. Salah satu tumbuhan yang
mengandung senyawa antioksidan adalah bayam
merah.
Bayam merah mengandung vitamin, protein,
karbohidrat, lemak, mineral, zat besi, magnesium,
mangan, kalium, dan kalsium. Vitamin yang terkandung
dalam bayam merah adalah vitamin A, C, dan E
(Syaifuddin, 2015). Bayam merah juga mengandung
komponen antioksidan, antara lain: betalain,
karotenoid, vitamin C, flavonoid, dan polifenol
(Wiyasihati dan Wigati, 2016).
Antioksidan merupakan molekul yang mampu
memperlambat atau mencegah oksidasi dari molekul
lain (Hamid, dkk., 2010).Salah satu jenis antioksidan
yang terkandung dalam bayam merah adalah flavonoid.
Flavonoid terdiri dari kelompok gabungan
polyphenolic yang memiliki struktur benzopyrone dan
banyak terdapat di bagian-bagian tumbuhan (Kumar
dan Pandey, 2013). Flavonoid merupakan senyawa
yang umumnya terdapat pada tumbuhan
berpembuluh.Flavonoid terdapat dalam tumbuhan
sebagai glikosida dan aglikon flavonoid.Biasanya dalam
menganalisis flavonoid, yang diperiksa adalah aglikon
dalam ekstrak tumbuhan yang sudah dihidrolisis (Lia,
2012). Agar bisa mendapatkan senyawa flavonoid pada
bayam merah, perlu dilakukan suatu metode proses
pemisahan yaitu ekstraksi.
Penelitian tentang aktivitas antioksidan dari
bayam merah sudah pernah dilakukan, tetapi
pengukuran kadar total flavonoid serta koefisien
perpindahan massa belum pernah diteliti sebelumnya.
Padahal data koefisien perpindahan massa sangat
diperlukan untuk keperluan perancangan alat
ekstraksi. Oleh karena itu, pada penelitian ini ingin
diketahui kadar total flavonoid serta nilai koefisien
perpindahan massa pada proses ekstraksi flavonoid
pada bayam merah yang dinyatakan dalam bilangan
Sherwood.
2. TEORI
Ekstraksi adalah kegiatan penarikan kandungan
kimia yang dapat larut sehingga terpisah dari bahan
yang tidak terlarut dengan pelarut cair (Erawati, 2012).
Mekanisme proses ekstraksi dimulai dari perpindahan
solven dari larutan ke permukaan solid (adsorpsi),
diikuti dengan difusi solven ke dalam solid dan
pelarutan solut oleh solven, kemudian difusi ikatan
solut-solven ke permukaan solid, dan desorpsi
campuran solut-solven dari permukaan solid ke dalam
badan pelarut (Pramudono, dkk., 2008). Proses
leaching sering digunakan untuk mengekstrak bagian
tanaman yang mengandung obat seperti akar, daun,
dan batang (Coulson dan Richardson, 2002). Faktor
penting yang mempengaruhi ekstraksi padat-cair
antara lain ukuran partikel, jenis pelarut, temperatur
dan pengadukan (Geankoplis, 2003). Pengadukan salah
satu faktor yang mempengaruhi proses ekstraksi
sehingga pada penelitian ini ingin diketahui bagaimana
pengaruh pengadukan terhadap kadar total flavonoid
yang didapat.
Perpindahan massa fasa cair-cair maupun padat-
cair merupakan suatu fenomena penting dalam proses
ekstraksi. Salah satu faktor yang mempengaruhi
kecepatan perpindahan massa adalah koefisien
perpindahan massa (Yulianto dkk., 2009).
Perpindahan massa pada ekstraksi padat cair
terjadi secara difusi. Difusi yaitu gerakan suatu
komponen melalui suatu campuran karena suatu
rangsangan fisika yang berlangsung dengan suatu
kecepatan tertentu. Pada awal proses konsentrasi
umpan dan pelarut berada pada keadaan tidak
setimbang yang mengakibatkan gaya dorong (driving
force) terjadinya difusi hingga keduanya mencapai
keadaan setimbang (Suhartono dkk., 2005).
Menurut Cussler, jumlah dari perpindahan massa
nya sebanding dengan perbedaan konsentrasi dan luas
area permukaan.
𝑁𝐴 = 𝐾𝐶 . 𝐴. (𝐶𝐴𝑆 − 𝐶𝐴 ) (1)
Pada proses ekstraksi padat-cair laju perpindahan
massa (N̅̅̅̅
A ) zat terlarut ke pelarut dengan volume V
dengan menggunakan suatu koefisien perpindahan
massa di mana CAS adalah konsentrasi jenuh dan CA
adalah konsentrasi pada waktu tertentu (Suhartono
dkk., 2005) dapat ditentukan dengan Persamaan :
V d(CA ) (2)
= ̅̅̅̅
NA = A K C (CAS − CA )
dt
dengan mengintegrasikan dari t = 0 dan CA = 0 sampai t
= t dan CA = CA,
𝐶𝐴
𝑑(𝐶𝐴 ) 𝐴 𝐾𝐶 𝑡 (3)
∫ = ∫ 𝑑𝑡
𝐶𝐴0 𝑑𝑡 𝑉 0
diperoleh :
𝐶 −𝐶 𝐾𝐶 𝐴 (4)
ln 𝐶 𝐴𝑆− 𝐶 𝐴 = − ( )𝑡
𝐴𝑆 𝐴𝑂 𝑉
𝐶 −𝐶
Dengan mengalurkan ln 𝐶 𝐴𝑆− 𝐶 𝐴 pada sumbu y dan
𝐴𝑆 𝐴𝑂
t pada sumbu x, maka KC sebagai koefisien perpindahan
zat terlarut (A) ke pelarut (B) yang diam dapat
ditentukan (Suhartono dkk., 2005).
Pada persamaan 4 , diasumsikan bahwa luas
permukaan padatan dalam bentuk potongan dan
dihitung menggunakan persamaan :
A=pxl (5)
Variabel-variabel yang mungkin mempengaruhi
koefisien transfer massa pada ekstraksi padat-cair
pada bejana berpengaduk adalah : ρ, μ, Ds, dp, N, db,
diameter dan tinggi baffle. Sedangkan dalam penelitian
ini variabel yang diperhatikan hanya ρ, μ, Ds, dp, N
sedangkan diameter butir (db) diambil konstan, dan
tidak digunakan baffle sebagai parameter, sehingga bila
dinyatakan dalam bilangan tak berdimensi dengan
memakai sistem MLT (Budi dan Sasongko, 2009) :
163
1400-Fm 9/9/99 7:37 AM Page i

Chemistry
Modern Analytical Chemistry

David Harvey
DePauw University

BostonBurr Ridge, IL Dubuque, IA Madison, WI New York San Francisco St. Louis
Bangkok Bogotá Caracas Lisbon London Madrid
Mexico City Milan New Delhi Seoul Singapore Sydney Taipei Toronto
1400-CH07 9/8/99 4:04 PM Page 215

Chapter 7 Obtaining and Preparing Samples for Analysis 215

Continuous extractions also can be accomplished with supercritical fluids.19 supercritical fluid
When a substance is heated above its critical temperature and pressure, it forms a A state of matter where a substance is
supercritical fluid whose properties are between those of a gas and a liquid. Super- held at a temperature and pressure that
critical fluids are better solvents than gases, making them a better reagent for ex- exceeds its critical temperature and
tractions. In addition, the viscosity of a supercritical fluid is significantly less than pressure.
that of a liquid solvent, allowing it to pass more readily through particulate samples.
One example of a supercritical extraction is the determination of total petroleum
hydrocarbons (TPHs) in soils, sediments, and sludges with supercritical CO2. Ap-
proximately 3 g of sample is placed in a 10-mL stainless steel cartridge, and super-
critical CO2, at a pressure of 340 atm and a temperature of 80 °C, is passed through
the cartridge for 30 min at flow rate of 1–2 mL/min. The petroleum hydrocarbons
are collected by passing the effluent from the cartridge through 3 mL of tetra-
chloroethylene at room temperature. At this temperature the CO2 reverts to the gas
phase and is released to the atmosphere.20

Chromatographic Separations In an extraction, the sample is initially present in

one phase, and the component of interest is extracted into a second phase. Separa-
tions can also be accomplished by continuously passing one sample-free phase,
called the mobile phase, over a second sample-free phase that remains fixed or sta-
tionary. The sample is then injected or placed into the mobile phase. As the sam-
ple’s components move with the mobile phase, they partition themselves between
the mobile and stationary phases. Those components having the largest partition
coefficients are more likely to move into the stationary phase, taking longer to pass
through the system. This is the basis of all chromatographic separation techniques.
As currently practiced, modern chromatography provides a means both of separat-
ing analytes and interferents and of performing a qualitative or quantitative analysis
of the analyte. For this reason a more thorough treatment of chromatography is
found in Chapter 12.

7G Liquid–Liquid Extractions
A liquid–liquid extraction is one of the most important separation techniques used
in environmental, clinical, and industrial laboratories. Two examples from envi-
ronmental analysis serve to illustrate its importance. Public drinking water supplies
are routinely monitored for trihalomethanes (CHCl3, CHBrCl2, CHBr2Cl, and
CHBr3) because of their known or suspected carcinogeneity. Before their analysis
by gas chromatography, trihalomethanes are separated from their aqueous matrix
by a liquid–liquid extraction using pentane.21 A liquid–liquid extraction is also
used in screening orange juice for the presence of organophosphorous pesticides. A
sample of orange juice is mixed with acetonitrite and filtered. Any organophospho-
rous pesticides that might be present in the filtrate are extracted with petroleum
ether before a gas chromatographic analysis.22
In a simple liquid–liquid extraction the solute is partitioned between two im-
miscible phases. In most cases one of the phases is aqueous, and the other phase is
an organic solvent such as diethyl ether or chloroform. Because the phases are im-
miscible, they form two layers, with the denser phase on the bottom. The solute is
initially present in one phase, but after extraction it is present in both phases. The
efficiency of a liquid–liquid extraction is determined by the equilibrium constant
for the solute’s partitioning between the two phases. Extraction efficiency is also in-
fluenced by any secondary reactions involving the solute. Examples of secondary re-
actions include acid–base and complexation equilibria.
6.2 Henry’s Law and Dilute Nonelectrolyte Solutions 251

pressure of exactly 1 bar, for this standard state. If the pressure on the solution is greatly
different from 1 bar, this would require a small correction term like that in Eq. (6.1-5),
which we neglect. Since the solvent obeys Raoult’s law if the solute obeys Henry’s law,
the standard state for the solvent in a dilute solution is the same as for a component of
an ideal solution. It is the pure solvent at a pressure equal to P ◦ .

Distribution of a Dilute Solute between Two

Solvents. Extraction
Consider the equilibration of two solutions containing the same solute but with different
solvents that are nearly insoluble in each other. For example, if I2 is dissolved in water
most of the I2 can be extracted from the water by equilibrating this phase with carbon
tetrachloride. For dilute solutions, it is found experimentally that the equilibrium mole
fraction of I2 in the water phase is proportional to the mole fraction of I2 in the carbon
tetrachloride phase. This fact is called Nernst’s distribution law. For a solute i and two
phases denoted by A and B, this empirical law is given by

(B)
xi,eq
Kd  (A)
(Nernst’s distribution law) (6.2-4)
xi,eq

(A) (B)
where xi,eq is the equilibrium mole fraction of the solute in phase A and xi,eq is the
equilibrium mole fraction of the solute in phase B. The constant Kd is called the
distribution constant or distribution coefficient. For a given solute, the value of Kd
depends on temperature and on the identities of the two solvents.
We now show that Nernst’s distribution law is valid for solutions that obey Henry’s
law and obtain a formula for the distribution coefficient. The chemical potential of the
solute in the two phases is given by

(A) ◦(H,A) (A)

µi  µi + RT ln(xi,eq ) (6.2-5a)

and
(B) ◦(H,B) (B)
µi  µi + RT ln(xi,eq ) (6.2-5b)

At equilibrium,

(A) (B)
µi  µi (6.2-5c)

We solve Eq. (6.2-5a) for xi,A and solve Eq. (6.2-5b) for xi,B , and after using Eq. (6.2-3),
we can write
(B)  ◦(H,A) ◦(H,B)
 (A)
xi,eq µi − µi ki
Kd  (A)
 exp  (B)
(6.2-6)
xi,eq RT ki

where ki,A and ki,B are the Henry’s law constants for substance i in phases A and B,
respectively. The mole fraction of the solute is greater in the phase in which its Henry’s
law constant is smaller. Equilibrating the two phases allows the solute to be extracted
from the other phase.
 molecules
Article
Continuous or Batch Solid-Liquid Extraction of
Antioxidant Compounds from Seeds of Sterculia
apetala Plant and Kinetic Release Study
Federica Mosca 1 , Gádor Indra Hidalgo 2 ID
, Juliana Villasante 2 and María Pilar Almajano 2, * ID

1 Polytechnic of Milan, Department of Chemistry, Materials and Chemical Engineering “Giulio

Natta” (CMIC), Piazza Leonardo da Vinci, 32, 20133 Milan, Italy; moscafede@yahoo.it
2 Chemical Engineering Department, Universitat Politècnica de Catalunya, Av. Diagonal 647,
08028 Barcelona, Spain; chemicontact@gmail.com (G.I.H.); julianavillasante@gmail.com (J.V.)
* Correspondence: m.pilar.almajano@upc.edu; Tel.: +34-9-3401-6686

Academic Editor: Derek J. McPhee




Received: 28 June 2018; Accepted: 14 July 2018; Published: 18 July 2018


Abstract: This work has been intended to investigate the antioxidant properties of compounds
extracted from seeds of Sterculia apetala (a plant from Central America) in order to add further
results to the relatively poor existing literature on the beneficial properties of this plant. Different
extraction methodologies were used such as batch or continuous extraction conditions using water
or ethanol 50% as solvents. The kinetic study has allowed estimation of the effective diffusion
coefficients in a continuous solid-liquid extraction, highlighting the strict dependence of the diffusion
rate and temperature and kind of solvent, showing the highest diffusion rate with ethanol 50% at
60 ◦ C. The comparison between different techniques and two solvents led to the selection of water
as the best extraction solvent while batch mechanically-agitated extraction was the most efficient
mode, with the benefits of use of an environmental-friendly solvent and reduction in process time
to achieve a high amount of extracted phenolic compounds. The analysis techniques used were
ABTS and Folin-Ciocalteau methods to investigate the antioxidant activity and quantify the Total
Phenolic Content (TPC) respectively. Also, different fatty acids were extracted from Sterculia apetala
seeds and analysed by Gas Chromatography in order to quantify other interesting chemical species
besides antioxidants.

Keywords: continuous extraction; kinetic diffusion; natural antioxidant; Sterculia apetala; fatty acids

1. Introduction
Plants have always been consumed by mankind for their nutritional properties and medicinal
effects due to the presence of the wide variety of secondary metabolites: terpenes and terpenoids
(around 25,000), alkaloids (around 12,000) and phenolic compounds (around 8000) [1]. These bioactive
compounds have attracted interest and scientific research has focused on their extraction from
natural sources and application to cure diseases, improve health and increase value of nutraceuticals
and cosmetics, especially phenolic and flavonoid compounds, due to their antioxidant activity [2].
Antioxidant compounds are not only used as an active principle of certain drugs but their use has also
been extended to the food production industry. Many food ingredients contain unsaturated fatty acids
which are quite susceptible to deterioration by oxidation and the addition of selected antioxidants can
be a valuable solution to this problem [3]. Their protective effect causes a huge delay in the degradation
processes taking place after a certain period of storage, prolonging the conservation of quality and
dramatically increasing the shelf-life of foods. Synthetic phenolic antioxidants such as butylated

Molecules 2018, 23, 1759; doi:10.3390/molecules23071759 www.mdpi.com/journal/molecules

Molecules 2018, 23, 1759 6 of 12

2.3. TPC Obtained from a Continuous or Batch Solvent Extraction at Different Temperatures
A comparison between batch and continuous extraction is shown below (Table 3). The same
solvents (water and ethanol 50%) and the same temperatures (25 ◦ C and 60 ◦ C) but with different
extraction periods and particle size of the sample allow interesting considerations on the advantages
and disadvantages of the tested techniques.

Table 3. Comparison between the use of batch or continuous solid-liquid extraction in TPC obtainment
form Sterculia apetala seeds samples varying in particle size and extraction period.

Extraction Extraction Particle Size Temperature TPC (mg GAE/g

Time (h)
Solvent Methodology Diameter (mm) (◦ C) of Dry Sample)
Batch extraction ≤0.1 25 4 4.33 ± 0.24
(Stirring conditions) ≤0.1 60 1 3.7 ± 0.42
Water
7±1 25 6 2.57 ± 0.13
Continuous extraction
7±1 60 6 4.13 ± 0.14
Batch extraction ≤0.1 25 4 2.28 ± 0.31
(Stirring conditions) ≤0.1 60 1 3.08 ± 0.12
Ethanol 50%
7±1 25 6 2.37 ± 0.85
Continuous extraction
7±1 60 6 4.72 ± 1.34

Considering the differences between the behaviour of the two solvents in the batch extraction,
water provided better results at room temperature but a temperature increase seemed to be not so
beneficial while, for ethanol 50%, the increase in temperature improved a lot the solvating power and
gave a good TPC yield. Continuous extraction did not show any significant difference dependent
on the use of one solvent or the other at 25 ◦ C but the increase in temperature highly improved the
extraction power of ethanol 50% which achieved the highest results in extractable TPC per gram of
dry seeds. Water provided very good results with both batch and continuous extraction and at 25 ◦ C
the former led to a higher TPC content probably due to a weaker solvating power of water for the
antioxidant compounds of interest at this temperature in continuous solvent flow conditions (at this
specific rate of 1 mL/min). In batch conditions, the residence time is very long and solubility of solute,
good stirring, high mass transfer and high contact surface area seem to be adequate conditions for
reaching equilibrium concentration in at least 4 h. Water extraction in the optimum conditions in terms
of cost and time (25 ◦ C for 4 h) yielded twice the TPC obtained in the same conditions with ethanol 50%
and only with a temperature increase (up to 60 ◦ C), was it found that ethanol 50% provided comparable
results to those obtained with water. An interesting observation is the totally different trend of extraction
power: increasing the temperature and reducing the extraction time, water showed a decrease results
reaching the best yield with the severest conditions (60 ◦ C for 1 h), even if the yield was still lower
than that obtained with water at room temperature. This could be explained by the fact that pure hot
water could favour the solubility of polyphenols and other molecules with similar characteristics to
polyphenols (such as anthocyanins, tannins, saponins and terpenoids [1]) lowering their extraction rate
and generating interferences in the Folin-Ciocalteau analysis. The increase in temperature could also lead
to instability and thermal degradation of antioxidant molecules, significantly reducing the detected TPC.
Pure water selectivity towards target molecules (polyphenols) is high at low temperatures (25 ◦ C) but
decreases for higher values (60 ◦ C) while its solvating power greatly increases. Ethanol, despite the lower
solvating power, shows good selectivity with respect to polyphenols mainly at higher temperature [15].
Based on further performed tests, an increase in temperature of 56 ◦ C (test at 4 ◦ C and test at 60 ◦ C)
provides an improvement of 80% in yield of extracted TPC with ethanol 50% while the same increase
in temperature leads to a drop of 26% in yield of extracted TPC with water.
There are very few previous studies regarding this topic. One that could be highlighted is from
Fontoura et al. (2015) who performed extraction of polyphenols from Sterculia apetala bark and gave a
value of TPC of 59.7 ± 13.9 GAE mg/g of sample using Ultrasound extraction (for 60 min and 24 h of
Molecules 2018, 23, 1759 11 of 12

were placed on a magnetic stirrer/heater and the extraction was performed at 25 ◦ C for 4 h or at 60 ◦ C
for 1 h (to avoid an excessive thermal degradation of the sample).

3.7. Fatty Acid Extraction

The precise weight of empty plastic vials was measured using an analytical balance with high
precision (5 decimals) and then, previously frozen and crushed seeds were placed into n-hexane to
perform the extraction, following a proportion of 1 g/6 mL of solvent. The vials were covered with
pitted parafilm (permeable) and left for at least five days to allow complete extraction of fatty acids
by hexane, followed by its total evaporation. Once fatty acids were extracted and deposited on the
bottom of the vial, seeds were removed and vials weighed again to compare with the weight of the
empty ones and to measure the amount of the extracted fatty acids. Fatty acid methyl esters (s) were
recovered using methodology described in literature with modifications [23,24]: 0.1 g of extract was
esterified by saponification using 200 µL of KOH solution in methanol (2 M) and fatty acids were
recovered by adding to 2 mL of n-hexane. Finally, samples were centrifuged at 2000 g for 10 min and
the supernatant was kept at −80 ◦ C until analysis.

4. Conclusions
Different methods for extracting antioxidant compounds from seeds of Sterculia apetala have been
studied. Batch solvent extraction under continuous stirring is likely to be the most used, cheap and
easy method for the extraction of antioxidant compounds from natural raw materials. An increase in
temperature up to 60 ◦ C increases the diffusion rate and achieves a good solvating power. Water has
consistently led to better extraction than ethanol 50%. Considering all aspects including convenience,
batch extraction with continuous stirring at room temperature using water as solvent and seeds
ground to a powder are the optimal conditions to obtain the best yield of antioxidant compounds from
Sterculia apetala seeds. Moreover, a continuous process requires the use of an extraction apparatus
made of different units involving the presence of peristaltic pumps, an extraction column and a solvent
bath. There is limited literature research on this kind of plant and previously studies were related
to the investigation of the antioxidant properties of samples of bark or leaves of different varieties
of Sterculia. Comparing our values with the literature, it is clear that seeds contain less antioxidant
compounds than other plant parts but also the kind of extraction technique, the solvent used and the
analysis methods are important factors affecting the comparison. Sterculia apetala seeds seem not to be
a major source of antioxidant compounds compared to many other plants [16].

Author Contributions: M.P.A. conceived the idea, designed and led the experiments and coordinated the authors.
F.M. performed the experiments, analysed the data and wrote the manuscript. G.I.H. and J.V. collaborated in the
performance of the experiments and review of the manuscript. All authors read and approved the final manuscript.
Funding: This research received no external funding.
Acknowledgments: Authors would like to thank Michael H. Gordon for the English correction.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Azmir, J.; Zaidul, I.S.; Rahman, M.M.; Sharif, K.M.; Mohamed, A.; Sahena, F.; Jahurul, M.H.; Ghafoor, K.;
Norulaini, N.A.; Omar, A.K. Techniques for extraction of bioactive compounds from plant materials: A review.
J. Food Eng. 2013, 117, 426–436. [CrossRef]
2. Azwanida, N.N. A Review on the Extraction Methods Use in Medicinal Plants, Principle, Strength and
Limitation. Med. Aromat. Plants 2015, 4, 1–8.
3. Brewer, M.S. Natural Antioxidants: Sources, Compounds, Mechanisms of Action, and Potential Applications.
Compr. Rev. Food Sci. Food Saf. 2011, 10, 221–247. [CrossRef]
4. Da Silva, R.P.F.F.; Rocha-Santos, Teresa A.P.; Duarte, Armando C. Supercritical fluid extraction of bioactive
compounds. Trends Anal. Chem. 2016, 76, 40–51. [CrossRef]
 Available online at www.joac.info
ISSN: 2278-1862

Journal of Applicable Chemistry

2014, 3 (4):1329-1336
(International Peer Reviewed Journal)

A Chemical Education Article-

Statistical comparison of results of redox titrations using K 2Cr2O7
and KIO3 in the undergraduate analytical chemistry lab
1 1,2
David W. Randall * and Luis K. Garibay

1. Andrews University, Department of Chemistry & Biochemistry, 4270 Administration Drive,

Berrien Springs,MI 49104 USA
2. Current address: Department of Chemistry, University of California, Davis, CA 95616 USA

Email: randalld@andrews.edu

Accepted on 12th July 2014

_____________________________________________________________________________
ABSTRACT
Reducing the quantity of hazardous substances used and hazardous waste generated by under-
graduate laboratory experiments is important. However, simply replacing hazardous compounds
with less hazardous reagents may not retain the pedagogical (or analytical) goal of the experiment
if the chemistry does not fundamentally work. We evaluated several literature-based replacement
oxidants for K2Cr2O7 (potassium dichromate) and identified KIO3 (potassium iodate) as the only che-
mically viable alternative for thiosulfate standardizations, consistent with use of iodate by others. Using
ANOVA analysis, two years of student results where K 2 Cr2O7 was used as the oxidant were compared with
two years of student results where KIO3 was used as the oxidant (ANOVA -value for precision =
0.684; ANOVA -value for accuracy = 0.638). This comparison of multiple years of student data
enabled us to confidently eliminate toxic Cr(VI) from a quantitative iodometric titration in our second
year analytical chemistry laboratory, while students maintained a high level of both accuracy and
precision.

Keywords: Green Chemistry, Analytical Chemistry Education, Safety / Hazards, Titration / Volumetric
Analysis.
______________________________________________________________________________

INTRODUCTION

Redox titrations remain important components of an analytical chemistry laboratory curriculum, because
this relatively straightforward method gives high-precision results with experimentally-determined
uncertainty in the 4th digit. Such attainable precision facilitates the development of a common
student learning objective for analytical chemistry: producing results that are both precise and
accurate[1]. Potassium dichromate (K 2Cr2O7) is a common oxidant in redox titrations due to many
desirable characteristics as a primary standard: stable to oven drying and storage in ambient conditions;
widely availability; solubility in water; relatively low cost; and high molecular weight. However, the
dichromate anion contains Cr(VI) (hexavalent chromium) which is carcinogenic, toxic, and genotoxic.[2-
5] Historically, the “chemical convenience” of this chemical outweighed concerns about its hazardous

1329
David W. Randall et al Journal of Applicable Chemistry, 2014, 3 (4): 1329-1336

nature. The green chemistry principles that have emerged in the last two decades attempted to find
chemically viable processes with a reduced environmental impact.[6-7] As we educate future chemists, it
seems obligatory to consider these principles as we design laboratory activities for our students. In the
past 20 years, in chemical education much green chemistry attention has focused on organic chemistry
with a move towards less noxious solvents, reagents, and microscale synthesis.[8-12] While organic
chemistry has received considerable attention,[13-17] other courses in the chemistry curriculum can also
benefit from application of the 12 green chemistry principles,[18-23] including analytical chemistry.[24-
25] Asakai, et al [26] showed that KIO3 could replace K2Cr2O7 in redox titrations and evaluated other
oxidants, as well.[27] Given this and that IO3– is documented in textbooks and lab manuals available on
the web.[28-33] we have not “discovered” that KIO3 is a useful redox primary standard in educational
settings. Rather, this report compares the accuracy and precision of iodometric titrations using K2Cr2O7
as a primary oxidant for two years with iodometric titrations using KIO3 as a primary standard for two
years when used by second or third year chemistry and biochemistry students.

MATERIALS AND METHODS

Chemical Methodology
Standardization of Thiosulfate: The general approach of thiosulfate / iodometric titrations is outlined in
analytical chemistry textbooks.[34-35] Eq. 1 shows that when a known quantity of primary oxidant [Ox],
classically K2Cr2O7, reacts with an excess of iodide (from KI) in acidic solution (pH ~0.5) to generate
iodine (I2) stoichiometrically. Eq.2 shows that in the presence of excess iodide (I–), triiodide (I3–) was
thermodynamically favored.[36-37] Finally, Eq.3 shows triiodide reacting with the student-prepared
sodium thiosulfate (Na2S2O3) solution to be standardized. The oxidant was the limiting reagent (reactant)
and was stoichiometrically related to thiosulfate.[38]

[Ox](aq) + 2I– (aq) → [Ox]reduced(aq)+ I2 (aq) .......................1

I– (aq) + I2 (aq) ⇌ I3– (aq) Keq ≥ 7 × 102 @ 25 °C [39] .............2

2 S2O32– (aq) + I3– (aq) → 3I– (aq)+ S4O62– (aq) ........................3

Oven-dried (150°C for ≥ 90 min), analytically-massed quantities (~100s of mg) of oxidant were added to a
250 or 500 mL Erlenmeyer flask and dissolved in 25-50 mL of distilled or deionized water. A second
solution contained a stoichiometric excess of KI dissolved in 25-50 mL of distilled water and ~1-2 mL of 6
M HCl. The oxidant and KI solutions were mixed immediately before beginning the titration and I 2
(or I3–) forms rapidly, which was titrated with the student's thiosulfate solution. The titration was
performed relatively quickly because atmospheric oxygen can react with excess iodide in acid to form I 2
(or I3–), which would interfere with the analysis. Citrate, added when the oxidant was K 2Cr2O7, complexed
with Cr3+ which further drives the set of titration reactions to the right. Starch indicator was added before
the end point was reached, but only after the I 2 (or I3–) concentration has been significantly diminished and
the solution lightens to light reddish-brown. The titration end point goes from blue to colorless. Ten
students used approx. 9 grams of toxic K2Cr2O7 and produced ~15 liters of ~5mM Cr(III), which were
managed in a costly, separate waste stream.

Precisely reaching the end point of the titration when using K 2Cr2O7 was complicated by the fact that the
Cr(III) citrate complex ion was light blue in color which was somewhat difficult to distinguish from
a low concentration starch , iodine solution. In contrast, iodate was colorless in both oxidized and
reduced states. For highly precise work it was not possible to prepare a stock solution of I 2 (or I3–), rather,
the stoichiometric quantity of iodine was prepared immediately before each titration.[40]
Chemicals and Equipment: Reagents were used as supplied by a variety of typical academic chemical
vendors. Students prepared solutions in standard volumetric glassware with pre-boiled deionized or
1330
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