Alghanmi
3
Learning Resources
QUANTITIVE CHEMICAL ANALYSIS
D. Harris 8th ed.
ANALYTICAL CHEMISTRY. Gary D. Christian. Fifth Ed. JOHN
WILEY & SONS, INC.
Note of Lab.
Assessment summary
Assessment
Due Date Weighting
Task
Exam 1 The sixth week 15%
Exam 2 The twelfth week 15%
Quizzes The fourth, tenth and 10%
fifteenth weeks
Lab All weeks 20%
Final Exam Examination period 40%
Summation 100%
4
5
Extraction is the transfer of a solute from one phase to another.
Solvent extraction involves the distribution of solute between two immiscible liquid
phase.
The reasons to use an extraction in analytical chemistry are to isolate or
concentrate the desired analyte or separate it from species that would interfere in the
analysis.
This technique is extremely useful for very rapid and clean separations of both
organic and inorganic substances.
The most common case is the extraction of an aqueous solution with an organic
solvent.
[ S ]1
KD
[ S ]2
where:
KD is the distribution coefficient
Solvent 1 is an organic solvent
Solvent 2 is a water
If the KD large, the solute will tend toward
quantitative distribution in solvent 1.
Where e represents the ether solvent and a represents the aqueous solvent.
Part of the benzoic acid in the aqueous layer will exist as Bz-, depending on the
magnitude of Ka and on the pH of the aqueous layer; hence, quantitative
separation may not be achieved.
D
s o
s a
In benzoic acid example it is given by
[ HBz ]e
D
[ HBz ]a [ Bz ]a
[ HBz]e K D [ HBz]a
K D [ HBz ]a
D
[ HBz ]a K a [ HBz ]a /[ H ]a
KD
D
1 K a /[ H ]a
Prof. Dr. Khairia Al-Ahmary &
12
Dr Reem Alghanmi 2016
KD
D
From the Eq. it is clear that: 1 K a /[ H ]a
If [H+]a Ka, D is nearly equal to KD
If KD is large, the benzoic acid will be extracted into ether layer and D is
maximum under these conditions.
If, [H+]a Ka, then D reduces to KD[H+]a/Ka, which will be small, and the benzoic
acid will remain in the aqueous layer.
That is, in alkaline solution, the benzoic acid is ionized and cannot be extracted,
while in acid solution, it is largely undissociated.
These conclusions are what we would intuitively expect from inspection of the
chemical equilibria.
It is clear that the extraction efficiency will be independent of the original
concentration of the solute.
This is one of the attractive features of solvent extraction; it is applicable to tracer
levels and to macro levels alike, a condition that applies only so long as the
solubility of the solute in one of the phrases is not exceeded and there are no side
reactions such as dimerization of extracted solute.
mmol Molarity mL
Prof. Dr. Khairia Al-Ahmary &
15
Dr Reem Alghanmi 2016
The percent extracted is given by
[ S ]o Vo
%E 100%
[ S ]o Vo [ S ]a Va
where Vo and Va are the volumes of the organic and aqueous phases, respectively.
It can be shown from this eq. that the percent extracted is related to the distribution
ratio by
100 D
%E
D (Va / Vo )
If Va = Vo then
100 D
%E
D 1
In the case of equal volumes, the solute can be considered quantitatively retained if
D is less than 0.001. It is essentially quantitatively extracted if D is greater than
1000. The percent extracted changes only from 99.5% to 99.9% when D is
increased from 200 to 1000.
Shows that the fraction extracted can be increased by decreasing the ratio of
Va/Vo, for example, by increasing the organic phase volume.
A more efficient way of increasing the amount extracted using the same
volume of organic solvent is to perform successive extractions with smaller
individual volumes of organic solvent.
D
s o 0.15
D 6
s a 0.025
Ion-Association
Metal Chelates
Complexes
The mechanism:
The chloro complex of iron is coordinated with oxygen atom of the solvent
(the solvent displaces the coordinated water), and this ion associates with a
solvent molecule that is coordinated with proton:
C H O : H
2 5 2
, FeCl 4 [(C2 H 5 ) 2 O] 2
Prof. Dr. Khairia Al-Ahmary &
23
Dr Reem Alghanmi 2016
The uranyl ion UO22+ is extracted from aqueous nitrate solution into
isobutanol by associating with two nitrate ions
(UO22 , 2 NO3 )
with the uranium probably being solvated by the solvent to make it solvent-
like.
[(C6 H 5 ) 4 As , MnO4 ]
1M
UO2(NO3)2
(yellow)
Example:
Diphenylthiocarbzone (dithizone), which forms a chelate with lead ion.
KDHR and KDMRn are the distribution coefficients of the reagent and the
chelate, respectively
Ka is the ionization constant of the reagent
Kf is the formation constant of the chelate.
The distribution ratio is independent of the concentration of the solute (metal ion).
The more stable the chelate (the larger the Kf ), the greater the extraction
efficiency.
So, the separation efficiency depends on the relative formation constants and
on the relative solubilities of the chelates.
will not form a complex with aluminum because the added methyl group
dose not allow room for three molecules to group around this small ion.
Therefore, other metals can be extracted in the presence of aluminum with
this reagent.