SOLVENT EXTRACTION

Mohammed Rajai
BRITISH UNIVERSITY IN EGYPT
Abstract

The purpose of this experiment is to extract 0.1M ferric chloride from hydrochloric

acid using solvated complex diethyl ether. This is done by broughting aqueous iron solution

into contact with diethyl ether using iron having different concentration of HCL. The results

obtained in this experiment is tabulated clearly in Table 1 and Figure 3 so the Distribution

coefficient is calculated. Also a graph between Log K and Log CL which is the

concentrations of HCL was plotted in Figure 3 to clearly show the slope and the relation

between the distribution ratio and concentration.

1|Page Mohammed Rajai

Table of Contents
Abstract......................................................................................................................................1

Introduction................................................................................................................................4

Choice of solvent....................................................................................................................4

1. Distribution Coefficient..................................................................................................4

2. Selectivity (Separation Factor).......................................................................................5

3. Insolubility of Solvent....................................................................................................5

4. Recoverability................................................................................................................5

5. Density...........................................................................................................................5

6. Interfacial Tension..........................................................................................................6

7. Chemical Reactivity.......................................................................................................6

8. Viscosity, Vapour Pressure, Freezing Point....................................................................6

9. Availability and Cost......................................................................................................6

APPLICATIONS....................................................................................................................7

Ore Processing...................................................................................................................7

Nitric Acid Leach Liquors..................................................................................................8

Acid Treatment...................................................................................................................8

Alkali Treatment.................................................................................................................9

Spectrophotometric Determination of Iron..........................................................................11

Experimental results.................................................................................................................13

Experimental procedures..........................................................................................................14

2|Page Mohammed Rajai

Discussion................................................................................................................................14

Conclusion................................................................................................................................17

3|Page Mohammed Rajai

List of Tables

Table 1Experimental Results....................................................................................................15

4|Page Mohammed Rajai

List of Figures

Figure 1 Acid treatment by solvent extraction.........................................................................12

Figure 2 flow sheet of monazite processing by alkali treatment.............................................14

Figure 3 Log[k] vs Log [Cl].....................................................................................................17

5|Page Mohammed Rajai

Introduction

“ Ferric chloride solution is used as a leaching agent for sulfide minerals and an etching

agent for nickel lead frames owing to its strong oxidizing property. Several studies have been

performed on the ionic equilibria of FeCl3 in chloride solution. As ferric ions tend to form

complexes with chloride ion such as FeCl3 and FeCl4. FeCl3 can be regenerated from spent

FeCl3 solution by employing a solvent extraction method with a neutral or anion exchange

extractants .[ CITATION ERo63 \l 2057 ]

”

Choice of solvent

The solvent is the key to a successful separation by liquid-liquid extraction. The several

criteria are:

1. Distribution Coefficient

“ This is the ratio (at equilibrium) of the concentration of solute in the extract and

raffinate phases. It gives a measure of the affinity of the solute for the two phases. A

distribution coefficient other than unity implies that the solute must have different affinity in

the two phases. If only one solute is involved (such as in the recovery of an impurity from an

effluent stream), only the distribution coefficient need be considered, and it is desirable for

this to be as large as possible .[ CITATION ERo63 \l 2057 ]

”

6|Page Mohammed Rajai

2. Selectivity (Separation Factor)

“ If there are more than one solutes (say two solutes A and B), then consideration

should be given to the selectivity of the solvent for solute A as against B. The selectivity

between the 2 solutes A and B is defined as the ratio of the distribution coefficient of A to the

distribution coefficient of B. For all useful extraction operation the selectivity must exceed

unity. If the selectivity is unity, no separation is possible .[ CITATION ERo63 \l 2057 ]

”

3. Insolubility of Solvent

“ The solvent should have low solubility in the feed solution, otherwise the separation

is not "clean". For example, if there is significant solubility of solvent in the raffinate stream,

an additional separation step is required to recover the solvent .[ CITATION ERo63 \l 2057 ]
”

4. Recoverability

“ It is always necessary to recover the solvent for re-use, and this must ordinarily be

done by other means, eg. distillation. If distillation is to be used, the solvent should form no

azeotrope with the extracted solute and mixtures should show high relative volatility. The

solvent should also be thermally-stable under the distillation temperature .[ CITATION ERo63
”

\l 2057 ]

5. Density

“ A large difference in density between extract and raffinate phases permits high

capacities in equipment. This is especially important for extraction devices utilizing gravity

for phase separation.[ CITATION ERo63 \l 2057 ] ”

7|Page Mohammed Rajai

6. Interfacial Tension

“ The larger the interfacial tension, the more readily coalescence of emulsions will

occur but the more difficult the dispersion of one liquid in the other will be. The more readily

coalesces the emulsions the easier phase separation will be. Low interfacial tension aids

dispersion and thus improves contacting mass-transfer efficiency. Coalescence is usually of

greater importance, and interfacial tension should therefore be high .[ CITATION ERo63 \l
”

2057 ] ”

7. Chemical Reactivity

“ The solvent should be stable chemically and inert toward the other components of the

system and toward the common materials of construction .[ CITATION ERo63 \l 2057 ]
”

8. Viscosity, Vapour Pressure, Freezing Point

“ These should be low for ease in handling and storage, for example, a high viscosity

leads to difficulties with pumping, dispersion and mass-transfer rate.[ CITATION ERo63 \l

2057 ] ”

9. Availability and Cost

“ An excellent solvent may not be commercially available. Or it may represent a large

initial cost for charging the system, and a heavy continuing expense for replacing inevitable

operating losses.[ CITATION ERo63 \l 2057 ] ”

8|Page Mohammed Rajai

APPLICATIONS

“ Solvent extraction (SX) was employed mainly as an analytical tool for the separation

and analysis of elements with very similar chemical properties. The discovery and isolation

of the lanthanide and actinide elements provided impetus for the further development of these

technologies. SX is applied nowadays in various industries. This is a classic method of

separation and concentration of metal ions from aqueous solutions. It is a selective, cost-

effective and uncomplicated chemical process applied in hydrometallurgical separation and

purification of various metals. The use of solvent extraction in hydrometallurgy extends to a

wide range of metals from different feeds including low-grade ore, scrap, waste leachates and

dilute aqueous solutions. The technology was used first in nuclear technology; then, some

high-value metals like precious group metals solvent extraction technologies became

commercially viable and were developed and used. After the development of selective

chelating extractants, the solvent extraction was able to compete with classical separation–

concentration operations in this field .[ CITATION Per98 \l 2057 ]

” ”

Ore Processing

Uranium

“ The process used for recovery of uranium from its ores depends on the nature of the

ore. All the processes include a leaching step that solubilizes the metal. Solvent extraction is

used most frequently for the recovery and purification of uranium from the leaching liquors.

Most uranium-bearing ores are readily leached in sulfuric acid and the uranium is recovered

by solvent extraction using amines or dialkylorganophosphorus acids. Phosphate ores are

leached in a mixture of sulfuric and phosphoric acids or in phosphoric acid alone. Hot nitric

acid has also been used as a lixiviant for uranium ores .[ CITATION Per98 \l 2057 ]
” ”

9|Page Mohammed Rajai

Nitric Acid Leach Liquors

“ High-grade uranium ores are sometimes leached in hot nitric acid, particularly when

significant amounts of radioactive elements such as thorium are present in the rock. Uranium

forms the uranyl nitrate species that can be extracted by a solvating mechanism using TBP,

forming the species UO2(NO3) (TBP). TBP extraction of uranium from nitric acid is also

practiced for the purification of uranium and for its recovery from irradiated nuclear fuel.

[ CITATION Per98 \l 2057 ] ”

10 | P a g e Mohammed Rajai
Acid Treatment

“ The sulfuric acid method had been used most extensively in the United States. With

this method, depending on the acid/ore ratio, temperature and concentration, either thorium or

the rare earths can be selectively solubilized or both thorium and rare earths totally

solubilized. Rare earths and thorium are subsequently recovered from the solution. The

processes available are shown in Figure 1. The process of rare earth recovery based on rare

earth double sulphate precipitation was largely developed by Pilkington and Wylie and has

found industrial application. Yttrium and the heavy rare earth double sulphates are quite

soluble and go with thorium. Even in the stepwise neutralization procedure investigated at

Ames, yttrium and the heavy rare earths are precipitated along with thorium as a basic

compound. The rare earths, however, are recoverable from the thorium fraction during

solvent extraction for the purification of thorium and uranium. Solvent extraction with TBP

from an aqueous 8 M nitric acid solution of thorium and mixed rare earths permits the

recovery of thorium, uranium, cerium and cerium-free rare earths. Other commercially

significant processes essentially involve precipitation of thorium pyrophosphate or basic salts

from the leach liquor and subsequent recovery of the rare earth in solution as double sulfates,

fluorides, or hydroxides or even selective solubilization of thorium in the ore treatment stage

itself. The sulfuric acid process does not yield pure products and is no longer in commercial

use .[ CITATION Per98 \l 2057 ]

” ”

11 | P a g e Mohammed Rajai
 Figure 1 Acid treatment by solvent extraction

Alkali Treatment

“ The phosphate content of the ore is recovered as a marketable by-product, trisodium

phosphate, at the beginning of the flow sheet, and this has been a major attraction for the

commercial use of this process. In this concern, a modified leaching and extraction process of

uranium from hydrous oxide cake of Egyptian monazite was developed (75). In this process,

a monazite sample is ground to mesh size 200–270, then digested by boiling with sodium

hydroxide (50%) for 4 hours at 140 °C and filtered at 80 °C. The filtrate can be recycled for

recovery of sodium phosphate and excess sodium hydroxide, whereas the precipitate is

washed with water and dried. The dried precipitate, which consists mainly of thorium and

rare earths as well as uranium hydrous oxides, was leached several times with alkaline

solution composed of sodium carbonate, sodium hydroxide and hydrogen peroxide to

separate uranium selectively .[ CITATION Per98 \l 2057 ]

”

12 | P a g e Mohammed Rajai
“ The solution is filtered and the filtrate containing uranium is diluted and shaken with 0.1 M

Aliquat-336 in kerosene containing octanol in one-stage solvent extraction to recover and

purify uranium. The resulted uranium which is mainly tricarbonate complex is precipitated as

hydroxide by decreasing pH of the solution with addition of nitric acid. Thorium and rare

earths precipitate is dissolved in 4 M nitric acid with heating. Thorium is extracted from the

above mixture by Aliquat-336 in kerosene, stripped by shaking with HCl solution and

precipitated as hydroxide by addition of ammonium hydroxide giving thorium. On the other

hand, cerium(III) is oxidized to its tetravalent state by addition of sodium bromate, extracted

by Aliquat336 in kerosene containing 1-octanol and stripped by shaking the organic phase

with diluted HNO3 solution and then precipitated as hydroxide by addition of ammonia. An

integrated schematic diagram displaying the whole process is shown in Figure 8. The aqueous

solution principally containing La, Nd and Y is subjected to solvent extraction using a

synergistic TOPO–TRPO mixture in kerosene in 2:1 O/A phase ratio at 25 °C. The organic

phase is stripped by H2SO4 in equimolar ratio to separate most of Y and then treated by HCl

as stripping agent to recover La and Nd. The organic layer is finally washed with water to

separate the remaining Y and then used for another cycle of extraction. Overall recovery of

yttrium from the strip liquors was about 94%, while it was 79% and 81% for La and Nd,

respectively. Yttrium was finally recovered from the solution as the oxalate and calcined to

oxide. The final product was found to contain 84.5% Y2O3 .[ CITATION Per98 \l 2057 ]
”

13 | P a g e Mohammed Rajai
 Figure 2 flow sheet of monazite processing by alkali treatment

Spectrophotometric Determination of Iron

“ Many investigations of chemical species involve the interaction between light and

matter. One class of these investigations, called absorbance spectrophotometry, involves the

transfer of energy from a photon of light to an analyte to produce an excited state species. By

accounting for the quantity of light absorbed, the amount of analyte can be determined.

Common analytical applications of spectrophotometry take advantage of the Beer-Lambert

Law (often simply called Beer’s Law) that relates the concentration of an analyte to its

absorbance of monochromatic radiation as shown below : ”

Equation 1

A=−logT =εbc

14 | P a g e Mohammed Rajai
“ Where A is absorbance, T is transmittance,  is a constant called the molar absorptivity, b is

the path length through the sample, c is analyte concentration. In practice, instruments

monitor the transmittance of light by comparing the amount of light that leaves the light

source, passes through the absorbing solution and strikes a detector (P) to the amount of light

that strikes the detector when a non-absorbing solution is in the beam path (P0). The ratio of

these responses is the transmittance (or percent transmittance) . ”

Equation 2

P P
T= ∨T =100 ×
Po Po

“ This ratio assumes that the response at the detector in the absence of any light is zero, which

if often not the case. Most detectors have a nonzero response, even if no light is striking the

detector, called the dark current (Pdark), which must be compensated for in order for the

transmittance (and absorbance) value to be meaningful . ”

Equation 3

P−P dark P−Pdark

T= ∨T =100 ×
P o−Pdark Po−P dark

“ Therefore, to make a useful measurement, the instrument must “know” three things the

response when no light strikes the detector (Pdark), the response when a blank is in the beam

path (P0), and the response when the sample is in the beam path (P). Ideally, Pdark and P0

are constant for a particular instrument under a particular set of conditions. Therefore, by

measuring P at a single wavelength for a series of analyte solutions of known concentration

and using P0 and Pdark to calculate the absorbance (or transmittance) it is possible prepare a

calibration curve for the analyte response . ”

15 | P a g e Mohammed Rajai
“ The Spectronic 20 is an example of a direct-reading, single-beam spectrophotometer. By

virtue of being direct-reading, spectrophotometers feature fast operation, and because of their

simple design they are relatively inexpensive and require a minimum of maintenance. They

are particularly well suited for spectrophotometric determinations of a single component at a

single wavelength where only moderate accuracy ( 1 to T) is required. The Spec-20 has

only three controls (1) an On/Off/0%T knob used to set zero percent transmittance when the

sample chamber is empty, (2) a 100% T knob used to set 100 percent transmittance when a

blank is in the sample chamber, and (3) a wavelength control used to set the desired

wavelength for the measurement. Output on the Spec -20 is through an analog display that

has both percent transmittance and absorbance scales. When recording data, it is wise to

record both transmittance and absorbance values .[ CITATION Per98 \l 2057 ]

”

Experimental results
XTable 1Experimental Results

HCL Vaq Feaq Vo [Fe]o K LogCL LogK

Concentration
2 35.6 0.142 1 0.004 0.02809 0.30103 -1.55145
4
4 17.2 0.068 14.1 0.0564 0.81976 0.60206 -0.08631
8 7
6 3.6 0.014 24.2 0.0968 6.72222 0.77815 0.82751
4 2 1 3
8 4.7 0.018 33.25 0.133 7.07446 0.90309 0.84969
8 8 4

16 | P a g e Mohammed Rajai
 1
f(x) = 4.24x - 2.73

0.5

0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
LogK

-0.5

-1

-1.5

-2
LogCL

Figure 3 Log[k] vs Log [Cl]

Experimental procedures

First of all, 20ml of ferric solution is poured n a clean laboratory funnel using pipete

to be mixed with diethyl ether. After pouring ferric solution on diethyl ether it has to be

shaked for 5 minutes. Moreover, aqueous layer is separated from organic layer and after that

solvent is recovered. Permanganate titration is used to determine the concentration of iron III

as well as the distribution ratio.

17 | P a g e Mohammed Rajai
Discussion

“ An extractant, is a substance primarily responsible for the transfer of a solute (here metal)

from one phase to the other. The extractant is dissolved in a suitable diluent and together act

as a solvent. The diluent is immiscible with other phase which is usually water. The extractant

reacts with the solute by solvation/chelation/ion pair formation etc to extract from the

aqueous phase. The distribution equilibrium between two phases is governed by Gibbs phase

rule, given by : ”

Equation 4

P+V =C +2

Where, P = is the number of phases, V = is the variance or degree of freedom and C = is the

number of components.

“ In solvent extraction, we have P=2 two phases namely aqueous and organic phase, the

component C=1. solute, in solvent and water phase and at constant tempreture and pressure

P=1, thus, we therefore have: 2+1=1+2 ”

“ According to Nernst distribution law, If [X]1 is concentration of solute in phase 1 and [X]2 is

the concentration of solute in phase 2 at equilibrium : ”

Equation 5

[ X]1
K D=
[ X]2

“ Where KD is called as the partition coefficient, this partition or distribution coefficient is

independent of the total solute concentration in either of the phases. In the above expression

for KD, we have not considered the activity coefficient of the species in the organic as well as

in the aqueous phase. We, therefore, use the term distribution ratio (D) to account for the total

concentration of species in the two phases . ”

18 | P a g e Mohammed Rajai
Distribution Ratio (D)

“ The distribution of a solute between two immiscible solvents in contact to each other can be

described by the distribution ratio D . ”

Equation 6

[ X]1
D=
[ X]2

“ Where [X] represents the stochiometric or formal concentration of a substance X and the

subscripts 1 and 2 refer to the two phases. Since in most cases, two-phase system is of

analytical interest, an organic solvent and aqueous are involved, D will be understood to be ; ”

Equation 7

[ X ] org
D=
[ X ] aq

“ The subscript org and aq refer to the organic and aqueous phases respectively. Distribution

ratio ‘D’ is dimensionless quantity, separation of two solutes by solvent extraction is

expressed by the term, separation factor (α), which is related to individual distribution ratios , ”

DA
a=
DB

“ DA and DB are the respective distribution ratios of solute A and B. In the simplest extraction

case, the distribution ratio is constant in accordance with the classical Nernst distribution law,

a solute will distribute itself between two essentially immiscible solvents so that at

equilibrium, the ratio of the concentrations of the solute in the two phases at a particular

temperature will be constant, provided the solute is not involved in chemical interactions in

either phases. For such a solute, then KD=D. Now in practical work, instead of using term

KD or D one prefers to use term percentage extraction (E) .[ CITATION Dek04 \l 2057 ]
”

19 | P a g e Mohammed Rajai
Conclusion

“ Solvent extraction should be considered as a desirable route for product recovery and

purification along with fractional crystallization and distillation. The ability to make

separations according to chemical type, rather than according to physical properties such as

freezing point or vapor pressure, is one of extraction’s major attractions. Energy frequently

can be saved in the recovery of valuable products from dilute broth solution since a small

quantity of a selective solvent can be used, and recovery from the concentrated extract is then

facilitated. Selectivity of potentially attractive solvents can frequently be determined from

simple shake-outs over the desired concentration range. From these distribution data, the

combinations of amount of solvent and Distribution coefficient can be calculated . ”

20 | P a g e Mohammed Rajai
References

Dekker, M. (2004). Sepration of Iron. In Marcel, Principles and Practices of Solvent

Extraction (p. 760). New York: M Cox.

E, R. (1963). Solvent Extraction. In E. Robert, Liqud Extraction (p. 621). New York:

McGraw-Hill.

Perry, R. H. (1998). Liquid-Liquid Extracton. In R. H, Perrys Chemical Engineers

Handbook. McGraw-Hill.

21 | P a g e Mohammed Rajai