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OCTOBER 1, 2010

  

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c  Elution chromatography is one columnar
 chromatography technique involving washing the
The classical titrimetric and gravimetric methods solute through a stationary phase by quantitative
have long been solely tantamount to analytical additions of the mobile phase.[2]
chemistry until the early Twentieth century.
Chemical analysis is such a trending pursuit that
analytical methodologies have been advancing In 1850, forty years prior to Arrhenius· proposal
exponentially.[1] Hence, instrumental methods for of the ionization theory, a primordial notion about
analysis were developed. This report features ion ion exchange was discovered by two Englishmen,
exchange chromatography as a chromatographic J.T. Way and H.S. Thompson. The concept was
instrumental method for analytical chemistry and described by the liberation of Calcium and
as a separation science. Magnesium ions by treating earths with
ammonium sulfate. Ion exchange is a meristem
Chromatography, as an instrumental method, henceforth.[3]
separates, identifies, determines and quantifies the
chemical components of a mixture. The impeccable promise for analysis of the ion
Methodologically, it can be planar using porous exchange concept underwent further harnessing.
paper support or columnar using narrow tube It was inculcated and formally tagged in
support. It is composed of a stationary phase that chromatography in 1905 by M. Tswett.[3] The term
is fixed in the support and the mobile phase that ´ion chromatographyµ has then been shortened
moves through the stationary phase. by the common usage of the acronym IC. It has
become a formidable advancement after its
formalization as a novel analytical method by
Small, Stevens and Bauman of the Dow Chemical Be guided that the discussions give more emphasis
Company. The technique was then on cation exchange columnar chromatography as
commercialized in 1975 by the Dionex it has been employed throughout the course of the
Corporation, the leader of ion-exchange experiment.
equipment today.[4]

The experiment aimed to determine the 


 cc 
concentration in ppm of Cu2+ in a given sample 
using IC as a separation technique. In the As its name suggests, ion exchange
experiment, Dowex 50 cation exchange resin was chromatography is a chromatographic science
the stationary phase and the solvent containing concerned with the separation of various type of
the analyte ion was the mobile phase. A column
charged species in a system. This system is usually
previously inserted with a wad of absorbent
cotton for resin support and packed with comprised of separate phases.Since it explicitly
sulfonated resin was kept hydrated with distilled meddles with ion exchange, to maintain the ionic
water washings in an improvised IC burette tube. integrity of the system, a stoichiometric reaction
A flow rate of 15 drops per minute was must be paramount at all analyses.[1]
maintained by precise manipulation of the
stopcock. The mobile phase was allowed to flow To further substantiate and affirm the importance
until the pH of the eluate = pH distilled water = of this stoichiometric ionic reaction, look intently
pH of 5. These particulates are discussed intently to these chemical equations
in the remainder of this report. 10 mL of the
analyte sample was then eluted to the (a)V nrSO3 ² H+ + Mn+ '(rSO3)nM + nH+
preconditioned column for three trials. Per trial,
(b)V 2rSO3 ² H+ + Cu2+ '(rSO3)2Cu + 2H+
the eluate was allowed to flow to a fresh
Erlenmeyer flask until its pH = 5. This fresh pool (c)V 2H+ + 2OH-' 2H2O
was then titrated with previously standardized
sodium hydroxide NaOH against a primary Equation (a) shows the general chemical reaction
standard KHP. Cu2+ concentration in ppm was in cationic exchange. (Anionic exchange works
then calculated using the titrimetric data. analogously except that OH- species are involved,
not H+). nrSO3 ² H+ refers to the sulfonatedcation
The copper cation was separated from the sample exchanger resin, Mn+refers to the metal /
at par with the displacement of hydrogen protons cationanalyte species, and H+ refers to the
from the column. Separation is made possible by
displaced proton ion. Most importantly, n refers
the adsorption of charged analyte molecules to
immobilized resin ion exchange function group of to that stoichiometric factor, the defining number
opposite charge. The displaced ions from the in our calculation.
column exist in a stoichiometric ratio or factor
with the analyte ion.[1] Hence, the displaced ion Equation (b) is the particular reaction in the
will be titrated and the calculated amount experiment. Dwelling on the stoichiometry of the
multiplied by the said propagated ratio or factor equation, for every 1 mole of copper II species, 2
will be the amount of analyte constituents. There moles of the cation exchanger reacts, therefore, 2
is an exchange of ions, hence the name, ´ion moles of H+ are displaced. These displaced H+ are
exchange chromatographyµ.
then titrated with any strong base, NaOH for
An intent discussion about IC, its processes, example, and both species react with each other in
chemical concepts, stoichiometric calculations for one-to-one correspondence.
analysis, limitations, conditions, separation phases
and other particulates are found in the remainder Therefore, twice the amount of OH- and
of this report. transitively twice the amount of H+ , is equal to
one amount of Cu 2+
Analogously, thrice of an amount of H+ is equal to liberation of H+. A modest rate of flow
one amount of Aluminum 3+. All of which can be neutralizes the turbulence and high fluid pressure
explained by the interplay of ionic charges during at the narrow end of the tube.[3]
the stoichiometric reaction.
"-The resin used is Dowex ² 50.Cation
Now grounded to the notion that the calculations exchanger contain sulfonic acid groups nSO3 ² H+
are dependent on that stoichiometric ratio, this attached / chelated to the aromatic ring of
working equation for determination of the amount insoluble inorganic molecule nR.[5]Gel-based
of Cu2+ concentration in a given sample is derived: resins are produced by polymerizing with usually
styrene-divinylbenzene S-DVB copolymer. The
(d)Ppm Cu2+ = cross linkages with the copolymer give the resin
physical strength to withstand subsequent ion
reactions. The spherical shape narrows particle
size allotment. The polymerization yields inactive
Now we have a stoichiometric foothold for the resins and must be activated. [4]
ion exchange process, we are now ready to look
intently on the explanations of the materials and ($!"!" ,% nrSO3².Inactive resins have
mechanism of IC at par with the experiment hydrophobic spheres and must be introduced to
performed (cationic exchange columnar sulfonic acid nrSO3 ² to expose the functional
chromatography). hydrophilic sites for exchange. As the resins react
with the acid, water forms and swells the beads
")) !")!"- Prior to conducting the IC, a making it a suitable medium for reaction. Other
set of parameters must be paramount and acids like carboxylic acid and other bases like
maintained throughout the duration of the quaternary ammonium can functionalize resins. [4]
experiment. That is why a pH of 5 (the pH of Notice that a resin functional group is written with
distilled water must be observed. A pH of 5 H+ written posteriorly (nrSO3 ² H+). This shows
means that the system is isocratic and therefore is that the resin is activated and the H+ are now
highly deprotonated from H+ after the cation ready to be exchanged with another cation species.
exchanger has fully reacted with the cationanalyte The resins are also perforated with microporesfor
(all H+ have been displaced and are now ready for liquid pathways to increase surface area of
titration with strong base). [4] adsorption. These pores are generated by
poragens like toluene.
|!##% ! $#!"($%-The stationary adsorbent
phase or the site of exchange, the column of '"!" ! #!"# " &#"' ,% 5 =
resins, must be solvated with deionized and 5<-Sulfuric acid is such a strong acid that it
distilled water. [4] prolongs the activity of the cation exchanger.
Divalent and Trivalent organic and carboxylic are
$ ('"!($),()"#$""'| (,- more strongly held making them a less activator
Impurities can accumulate on the column which for the resins. Their stronger cohesion prevents
reduce the ion exchange capacity and reacts the resin ions from approaching the ion exchange
drastically with the system chemicals. [4] sites.[4] Transition ions from the previous usage
of the resin might still be left in the column.
$!.  !($) !##( ,." 0-; ") <-/   ! 2/
Sulfuric acid displaces these cations as explained
)!   "(-Flow rate is crucial for the ion
by IC mechanism making the column isocratic
exchange to take place. Water is the medium for
and ready for another usage.
reaction. Rapid flow will never assure the
optimum completion of the reaction and the total
))!"!.-The resin must be hydrated at all #- The actual concentration per 10 mL
times. Water level should not fall below the resin sample was 1250. Table 4 shows the percent error
level.Aside from maintaining the isocracy of the of the experimental ppm value per group.
system, water solvates the system and serves as a
suitable medium for reaction to take place. It also
displaces entrapped gases. [4] The air pockets cause
 "#$ %&# ! !' #$ ()&#
pulsations in the flow and may react with the
 *  !
resins forming altered canals. These canals cause
apparent loss in column capacity and adsorptive
power.

,!" ! 6-Since the aforementioned


discussion states that ion exchange explicitly
depends on the ionic interactions, therefore, the
ionic interactions are functions of ionic strength.
Separation is possible due to the differences in
ionic strength.Transition metals like Cu2+ has
greater ionic affinity with the sulfonic acidic
functional group of the cation exchanger than
H+, therefore, H+ is eluted first. 
Each group has less than 10% error. This further
!"-As mentioned, the liberated H+ are
affirms the feasibility and accuracy of IC in total
titrated with a strong base, NaOH to determine
ion concentration determination. Appendix C
the concentration of Cu 2+. Table 1 shows the
shows detailed data of statistics per group.
standardization data of titrant NaOH of all the
groups. !" ! | -Like any other instrumental
method and as a still growing chromatographic
It is grounded on the stoichiometric ratio that 1
science, IC is assailed with a few limitations. Table
mole Cu2+ = 2 moles H+. Therefore, using the
5 lists ions yet analyzable by IC
working equation (d), the concentration of Cu 2+
in ppm was determined per sample. See appendix +!&,-#&-.- 
B, table 2 for detailed titration data of trials 1, 2
and 3 per group. !##&-.
,!%-&)#/)*#)*,
  ! ))%#

 $!,$!&#,
)#)!#)%#)%%)/
c
#$-&/))&
!&/))&
One notable disadvantage is that IC is costly. The
class improvised a burette type IC tube. Amidst
the greater accuracy than that of classical methods,
IC, like any other instrumental titration, has many
demands and conditions to be observed.
An IC setup may encounter chromatographic c 

anomalies. An example is water dip, otherwise
known as carbonate water dip. There are also Upon intent analysis of the data, it can be
minor shifts in retention and calibration curves. concluded that since the class has a very small
amount of pooled standard deviation (9.86ppm),
Temperature must also be kept constant since the class garnered a very precise result. The class
minor fluctuations can alter the ionic kinetic got an accurate result basing on the substantially
energy. There are times that to maintain the low percent error of 0.8% with the reported class
isocracy, a buffer is needed. However, buffer may value of 1260 ppm. It can be induced that the
react with the resin or even the solvent containing interval in which, taking into account the
the analyte. Themethod provides no direct confidence level, the value of the Cu 2+
concentration from finite number of sources lies is
information on events occurring at the surface of
in 1260±7.59 ppm.
the stationary phase, because the ion-exchange
equilibrium is always determined by the balance The veracity and feasibility of IC can be affirmed
between the H+ and analyte ion interaction with basing from the experiment results. It can be
active sites of a resin. Impurities may also affect concluded that the total ion concentration can be
the data. These limitations may have lead to these accurately determined via IC, and that the
statistical deviations. However, the standard mechanism of isocracy of ionic charges and
stoichiometric ratio are of vital importance for
deviations per group are very minimal and can still
calculations involving IC. The highly accurate
substantiate the feasibility of IC. Appendix C value affirms the feasibility of IC as a means of
shows more statistical data including standard and determining total ion concentration.
relative standard deviations and confidence
intervals.
   
The standard deviations were pooled and the
average ppm was computed. Table 6 shows the [1] Dyer A., Hudson MJ.,et al. 1993. X|!"
overall class statistics. &#"'!#>)+"#") $#!"?-The
Royal Society of Chemistry.
0,$!1,#$!*%,,,##),#)%,
[2] Skoog D., West D., et al. 1996.X(")"$
!"$%#$ % ;)!"?-Saunders College
Publishing

[3] Walton, Harold. 1976. X|!"&#"'


!!' %?-Dowen, Hutchinson & Ross, Inc.

[4] Smith, Frank. 1983. X##!|!"


!!' %?-Wiley-Interscience Publications

The class got a low percent error with respect to [5] Ballesteros J., CalejaHJ.,CarilloKJ.,et al. 2009
the actual concentration of 1250 ppm. The class ed. X"$%#$ % ,!!%
garnered a value of 1260 ppm (0.8% error). The "($?-University of the Philippines ² Diliman,
pooled sd is also substantially low, meaning, the Institute of Chemistry.
class got precise measurements. The actual
concentration of the Cu2+ lies in the interval
1260±7.59 ppm.

 

 

 

 

 

 

 

 

 

 

 

 

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