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QUANTITATIVE ANALYSIS OF A SOLUTION CONTAINING
COBALT AND COPPER

Reading: Harris, 8
th
Ed., Chapters 11, 20 and 22
Prelab Problems, Harris, 22-12, 22-18. For the first week, prepare a flow chart and
procedure for part I. What will you do in the first 20 minutes?
THIS LAB REQUIRES A FORMAL WRITTEN REPORT.

GENERAL INTRODUCTION
In this experiment, you will be given a solution containing an unknown amount of cobalt
and copper. In Part I, you will separate the ions on an anion exchange resin. Once the two
elements have been separated, you will analyze for the amount of cobalt and copper by
microwave plasma atomic emission spectroscopy in Part II.
PART I: SEPARATION OF COPPER AND COBALT BY ION EXCHANGE
A. Introduction
Ion exchange resins are insoluble materials that contain cations or anions that can be
exchanged. The resins typically consist of a framework held together by strong chemical bonds.
Positively or negatively charged functional groups are attached to this framework and each of
these groups carries an oppositely charged ion, called a counter ion, which is held by
electrostatic attraction. When an ion exchange resin is placed in contact with a solution
containing ions, the counter ions on the resin can be replaced by an equivalent number of ions
from the solution.
Ion exchange resins are used widely, especially in the biological sciences. In addition to
metals, many low molecular weight biochemical compounds, such as amino acids, nucleotides,
hormones, peptides, and carboxylic acids, can be separated. Also, ion exchange resins are used
as water softeners and deionizers, and to concentrate trace amounts of organic and inorganic
compounds. Synthetic ion exchange resins, incorporating various functional groups, are
available commercially. Lewis-acidic functional groups are effective as cation exchangers,
while Lewis-basic groups exchange anions. The most common resins contain sulfonic acid
2

groups (SO
3

H
+
), which are strongly acidic, or quaternary ammonium groups (NR
3
+
Cl

),
which are strong bases. These resins interact with ions in solution by simple exchange reactions:
Cation exchange: RSO
3

H
+
+ M
+
RSO
3

M
+
+ H
+

Anion exchange: R'NR
3
+
Cl

+ X
-
R'NR
3
+
X

+ Cl


The acidic and basic functional groups are attached to organic resins, or polymers,
because these materials are easy to synthesize with various functional groups attached. In
addition, these organic polymers are insoluble in water and relatively inert. One common cation
exchange resin is produced by co-polymerizing styrene and divinylbenzene to give a
hydrocarbon resin that is quite stable except in the presence of alkaline oxidizing agents. A
common anion exchange resin is produced by polymerizing formaldehyde and urea to give an
amine resin that is chemically stable except in strongly acidic solutions.
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
CH CH
2
styrene divinylbenzene
+

Figure 1. Co-polymerization of styrene and divinylbenzene to form a cross-linked polymer.
A simplified equation for the reaction of styrene and divinylbenzene appears in Figure 1,
above. The structure is repeated in three dimensions and consists of polystyrene chains cross-
linked together by divinylbenzene. The extent of cross-linking, which is determined by the
relative amounts of styrene and divinylbenzene, is important. Too much cross-linking will
produce a hard, brittle, impervious resin, while too little will allow the resin to disperse in
solution. With just the correct amount of cross-linking, the resin will swell in solution to give a
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sponge-like framework to which the negatively charged sulfonate groups are attached. The
mobile H
+
ions are then relatively free to move through the pores of the sponge.
When the sulfonated polystyrene cation exchange resin is placed in contact with a
solution containing metal cations M
+
, the M
+
ions compete with H
+
for a seat on the SO
3


functional groups of the resin. The ion which has the strongest attraction for the functional
group will be favored in this competition reaction. The equilibrium constant for exchanging H
+

with M
+
depends on a number of factors, but most notably on the size and charge of the hydrated
cation M
+
. Usually, the strength with which an ion is held in the resin increases with increasing
charge on the ion (e.g., Na
+
< Ca
+2
< Al
+3
) and decreasing size of the hydrated ion (e.g., Li
+
<
H
+
< NH
4
+
< K
+
< Cs
+
). The extent of exchange also depends on the nature of the resin and on
the dilution of the solution.
Ion exchange columns can be used to separate a mixture of ions because each ion will
have a different affinity for the resin. Suppose a solution containing a mixture of metal ions is
added to the top of a column of a cation exchange resin. Initially, each metal atom becomes
attached to a functional group, displacing the original counter ion. In order to elute and separate
the mixture of metal ions, a continuous flow of acid is passed through the column. The H
+
ions
in the eluting solution will compete with the metal ions for the available sites on the resin. As
the metal ions at the top of the column are replaced by H
+
, they move further down the column
where they are readsorbed. Eventually, these metal ions will come out in the solution at the
bottom of the column. Separation between the metal ions occurs because the ions which are
bound most weakly are dislodged first and move through the resin the fastest. The result of the
repeated process of exchange onto and off the resin is that the ions with the lowest affinity for
the resin come out of the bottom of the column first. The general name for this process is
column chromatography.
In contrast to the previous example, in this experiment you will separate cobalt(II) and
copper(II) ions in a 6 M HCl solution on an anion exchange column containing AG 1-X8 resin
in 3 M hydrochloric acid, which you will use as the eluent, these two metal ions are bound to
different numbers of Cl

ligands, and therefore have different charges. (See below.) The


different charges of the two complexes result in different affinities for the resin, and this provides
the basis for the separation.
To understand this in more detail, consider the stepwise addition of a monodentate ligand
L

(which forms only one bond to the metal) to a metal ion M


n+
. The formation of complexes
can be represented by a series of sequential reactions in which ligands add one at a time,
4

displacing water molecules as they do so. Each reaction has its own equilibrium constant. The
sum total of these reactions is:
M(H
2
O)
a
n+
+ b L

M(H
2
O)
a-b
(L)
b
m+
+ b H
2
O
The participation of the solvent is often taken for granted and is usually omitted from chemical
reactions describing complexation:
M + b L

ML
b
m+
For the particular ions of interest to us, Cu(II), Co(II), and Cl

, we need only consider b values


between 0 and 4, and the sequence of reactions is (M = Cu or Co):
M
2+
+ Cl

MCl
+
b = 1 K
1
MCl
+
+ Cl

MCl
2
b = 2 K
2

MCl
2
+ Cl

MCl
3

b = 3 K
3
MCl
3

+ Cl

MCl
4
2
b = 4 K
4

Table 1 lists values of stepwise stability constants for the metal-chloro complexes of interest to
us.
Table 1. Stepwise Stability Constants for Some Metal-Chloro Complexes
Metal Ion K
1
K
2
K
3
K
4
Cu(II) 30.2 11.0 1.7 0.35
Co(II) 0.17 0.010 1.8 2.8
Using the data in Table 1 and solving the simultaneous equations defined by the
equilibrium constants K
1
to K
4
, it is possible to calculate the relative amounts of each species
present in a solution of known chloride ion concentration. The results are plotted in Figures 2
and 3 for Cu(II) and Co(II), respectively, as fractional distribution curves. Recall that pCl

=
log
10
[Cl

], so the graphs cover chloride ion concentrations from 10 M on the left down to 10

4
M on the right. The differences between the curves for Cu(II) and Co(II) form the basis for our
scheme to separate Cu(II) and Co(II) on an ion exchange column.
Note that the net charges of the various complex ions change as the concentration of
chloride ions is changed, and at a given chloride ion concentration the relative concentrations of
the different complexes is not the same for the Cu(II) and the Co(II). For example, in Figures 2
and 3 a line has been drawn at pCl

= 0, at which concentration all four Cu(II) species are


present but only b = 0 and 1 are present for Co(II). By picking the right chloride ion
concentration, it is possible to have the Cu(II) species where b = 3 and 4 be the predominant
5

species in solution; these complex ions are anions with charges 1 and 2, respectively. At the
same chloride ion concentration, the predominant Co(II) species in the solution are those where b
= 0 and 1; these are cations with charges +1 and +2, respectively. Therefore, by using an ion
exchange resin, one type of complex ion can be made to exchange and will be held back on the
column, while the other type will pass through quickly.
Figure 2. Complexation of Cu(II) by chloride ion.
From the data shown in Figures 2 and 3, a chloride ion concentration of 3.0 M (pCl

=
0.5) will result in Co(II) species eluting first as cations, followed by the Cu(II) species eluting as
anions. Since these complex ions are strongly colored, the progress of the separation can be
followed visually. Once the Co(II) ions have left the column, the Cu(II) ions can be sped along
their way by converting them back to cations. This is done by injecting a sample of water at
the top of the column; as it passes through the region of the column where the Cu(II) has been
bound, the sudden decrease in [Cl

] turns the complex Cu(II) ions back to simple aqueous Cu


2+

which no longer bind to the resin. (Check Figure 2 to convince yourself of this.)
The rates of elution of the two metals are indicated by the movement of two bands down
the exchange column; the green band of the cobalt complex precedes the yellow band due to the
copper complex. The cobalt and copper are collected in separate flasks, and in Parts II and III
you will analyze for their concentrations. Figure 4 shows the experimental set-up for this
separation.
6


Figure 3. Complexation of Co(II) by chloride ion.

B. Experimental Procedure
1. Obtain an unknown solution. It will be in 6 M HCl and contain both copper(II) and
cobalt(II) ions in concentrations ranging from 100 mM to 300 mM. Remember to record
your unknown number in both your lab notebook and the unknown log book in the room.
2. Setup the column kit according to the instructions of your GSI. Add a slurry of the
AG 1-X8 resin in 3 M HCl to the column from a small beaker until the column is filled
nearly to the conical section. After the column is filled with the slurry, let the resin settle
into a bed at the bottom of the column. As the resin begins to settle you will see three
layers, a clear liquid layer, a cloudy liquid layer, and solid. Once the clear liquid layer is
about 0.25 you can begin the packing process.
a. Slowly open the stopcock and slowly turn on the vacuum until the clear liquid is
just above the solid then close the stopcock. (NOTE: a vacuum may not be needed
the first time, just opening the stopcock may be enough to pack the resin)
b. If there is room in your column add more slurry. If there is no room in your column
proceed to step c.
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c. Let the resin settle until you again see separate layers of clear liquid, cloudy liquid,
and solid
d. Repeat steps a-c until you have packed the column with resin to approximately the
17-19mL mark. As you get closer to having the column packed it will be more
difficult to distinguish between the clear liquid, cloudy liquid, and solid layers, but
you should ALWAYS have a small amount of liquid above the solid.
Do not rush the packing process or you risk getting bubbles in your column. If you get
bubbles, you will have to start over.
3. Rinse the plastic column walls with 3 M HCl to remove any resin particles stuck to the
walls above the top of the resin bed and allow the column to sit with the stopcock closed
while you prepare your glassware. The distribution of the metal ions on the column during
elution depends upon the concentration of HCl and the flow rate. Keep the resin bed filled
with 3 M HCl at all times. This will prevent air from getting trapped in the resin bed.
Trapped air can produce a channeled flow of eluent through the column, resulting in less
clearly defined bands of the ions on the resin.
4. Gather all the glassware and storage bottles you will use for the separation procedure. The
glassware you use to collect the samples as they come off of the column should be acid-
washed according to the following procedure:
a. rinse with a small amount (~3 mL) (50 %) HNO
3

dispose of in the
50% HNO
3
waste
b. rinse 3! with tap water drain dispose
c. rinse with a small amount (~3 mL) 10 % HCl dispose of in the 10%
HCl waste
d. rinse 3! with tap water drain dispose
e. rinse 2! with distilled water drain dispose
Glassware that should be acid washed include: 6 beakers (for copper collection), 3 100mL
volumetric flasks (for dilutions), 6 125mL plastic bottles (for copper and cobalt solution
storage), and 1 1mL volumetric pipet Note: in addition to acid washing your volumetric
pipet, you will need to rinse the pipet with small aliquots (~0.25mL) prior to use. The
NAIT Chemical Technology has a video of proper pipetting technique that you may find
useful.
http://www.youtube.com/watch?v=qorl6rKLmRs
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5. Approximately 45 minutes are required to collect the cobalt from a single separation. To
prepare the column for the addition of the unknown sample solution, open the stopcock and
permit the remaining liquid in the column to drain into a beaker until it has just reached the
surface of the resin, then close the stopcock. Do not let the liquid drain down into the resin
bed.
6. With the stopcock closed, accurately pipet 1.00mL of the unknown solution onto the resin
column, taking care to disturb the resin surface as little as possible. (One or two practice
tries with plain 3M HCl are a good idea at this point.) Dripping the solution (and
subsequent mobile phase additions) on the conical section, as opposed to directly on the
resin, is suggested to prevent disturbing the surface.
7. After adding 1mL of unknown, open the stopcock to permit the liquid in the column to
drain to the resin surface, then close the stopcock.
8. Using a plastic dropper carefully add about 1mL of 3M HCl onto the top of the resin, again
open the stopcock to drain to the resin surface, and then close the stopcock. Note: adding
more than 1-1.5mL of 3M HCl will cause poor separation.
9. , and continue adding 3M HCl in 1mL increments until the sample is completely on the
column. Once the sample is completely on the column, you can add more than 1mL
increments of 3M HCl to continuously separate the mixture. See the Tip Sheet for pictures.
Collect the eluent in a waste beaker until the blue-green band of cobalt approaches the
bottom of the column. Take care to not allow the resin to run dry.
10. As the ions move down the column, the blue-green cobalt band will precede the yellow
copper band. When the leading edge of the cobalt band approaches the end of the column,
begin collecting the eluent in a beaker and continue collection as long as the front of the
copper band has not reached the bottom of the column. (Note that the cobalt band, which
appears blue-green on the column, results in a pink solution as it exits the column.)
11. When the cobalt is approximately three-fourths removed from the column, close the
stopcock, and withdraw the bulk of the HCl above the resin. Add 2 ml of distilled water to
accelerate the elution of the copper band and allow it to drain to the resin surface. Once
again add 3 M HCl to continue elution. Adding the H
2
O lowers the HCl concentration
allowing the Cu to be eluted more rapidly.
9

12. When the copper band approaches the end of the column, collect the eluent containing the
copper in a beaker until two minutes after the yellow band can no longer be detected on the
column. (Note that the copper band, which appears yellow on the column, results in a
green solution as it exits the column.)
13. When the copper band is almost off the column, the next 1-ml portion of your unknown
sample can be added and the elution procedure repeated. Remember to use a fresh pair of
(acid-washed) collection vessels each time you perform the separation. You need three
data points. Following the described procedure, you should separate three unknown
samples in about 3 hours.
14. On the THIRD trial, after the cobalt has completely eluted off the column, you can flush
the column with water to quickly remove the copper. This method of removal should
only be used for the third trial.
15. Quantitatively transfer each copper solution to a 100-ml volumetric flask using distilled
water. Remember to rinse the beaker with small quantities of distilled water to provide a
quantitative transfer of the copper. Dilute the solution to the mark and invert several times
to create a homogenous solution. Transfer this solution into a labeled plastic bottle and save
for part II. Repeat this procedure for the cobalt solutions collected. You will need to
repeat the cleaning process of the 100-ml volumetric flasks prior to using for the cobalt
solutions. When you are done should have 6 plastics bottle, three of which are cobalt, and
three of which are copper. Store these bottles in your drawer until next week.

Clean Up
1. There are four waste containers; ask your GSI if you are unsure where to dispose your
waste:
a. Excess 3M HCl from elution (NO Copper NO Cobalt), just HCl. Pour the first
water rinse after the acid rinse here.
b. 50% Nitric Acid Wash ONLY used nitric acid wash (NO Copper NO Cobalt)
c. 10% HCl Acid Wash ONLY used hydrochloric acid wash (NO Copper No
Cobalt)
d. All Metals Solutions all other liquid waste
2. Extra unknown can be disposed of in the metals waste bottle, and the vial can go into the
blue containers in the room. DO NOT put used unknown back with unused unknowns.
10

3. Return all unused resin to the ISF window
4. Clean the column setup kit and return to the ISF window
5. Clean the 100mL volumetric flask and return to the ISF window
NOTES: Every year there are minor acid spills during this experiment. We recommend wearing
clothes you wont mind damaging.


Post Lab Questions
Answers to the following questions should be concisely recorded into your lab notebook to be
turned in at the beginning of lab the week of February 6-10.
1. What form of Cu and Co are being eluted?
2. Explain why you add water to the column between Co and Cu.
3. Imagine you repeat the experiment, but instead using 2M HCl. What would change? What
about 4M HCl?
4. What would be the effect of a narrower column? (ie: 1mm instead of 1cm) What would be the
effect of a longer column?
5. How many significant figures should your final measurement have?
6. In order to set up your column, you used a vacuum flask to increase the flow of solvent
through the stopcock. Why cant you accelerate the separation by applying a vacuum?
7. If next week, when you are titrating your three cobalt samples with EDTA, you find that your
samples contain the same amount of cobalt to less than one percent. Later, you discover that your
samples actually contain 25% less cobalt than they should have. What are two possible
explanations?