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Chemistry 26.

1
2 Written Laboratory Examination Reviewer
A.Y. 2010 2011
nd

Experiment # 8
QUANTITATIVE DETERMINATION OF TOTAL HARDNESS IN DRINKING WATER BY
COMPLEXOMETRIC EDTA TITRATION
INTRODUCTION
Primary Standard: Calcium Carbonate (CaCO 3)
Titrant: EDTA
Titrant/Analyte: Mineral Water Sample
Indicator: Eriochrome Black T (EBT)
Total hardness is a measure of the concentration of calcium and magnesium ions in water. It is,
however, measured primarily as ppm of calcium carbonate (CaCO3) due to the negligible
presence of other ions.
Ideal Freshwater Ca2+ Concentration: 10 250 ppm
Ideal Freshwater Mg2+ Concentration: 5 125 ppm
Choice of Titrant: Ethylenediaminetetraacetic acid (EDTA)
EDTA is set as the titrant due to its hexadentate property as a ligand in the formed metal-EDTA
complex. This means that it can bind with metal ions in a 1:1 ratio due to its numerous binding
sites, simplifying calculations.
It is important to note that EDTA exists in different states depending on the pH of the solution.
At pH 10, EDTA is represented as Y4- in equations.

A 1:1 ratio also means a sharper endpoint for the titration.

Choice of Indicator: Eriochrome Black T (EBT)


Eriochrome Black T (EBT) was used in the experiment to determine the endpoint of the EDTA
titration process. The color of the Metal-EBT complex in a pH 10 solution (due to ammonia
buffering) is wine red*. Upon reaching the endpoint, the complex is broken up and the solution
appears blue. Note that the charge of In is -3.
H2Y2- + MgIn- -> MgY2- + HIn2- + H+
wine red

blue

One limitation of the EBT indicator, however, is that it readily undergoes air oxidation, so the
solution must be covered when not in use. Calmagite is a possible substitute that, unlike EBT,
does not undergo air oxidation.

*For a pH value less than 6.3, the transition is wine red to red. (Hard to detect)
*For a pH value greater than 11.6, the transition is wine red to orange. (Hard to detect)
SOLUTIONS AND REAGENTS
Stock EDTA Solution
Standardization Ratio: 1 mol EDTA: 1 mol Ca 2+ (CaCO3 standard)
The solubility of EDTA crystals in water is quite limited as witnessed in the experiment. This is
why heat must be introduced while stirring to ease dissolution. Note that this is an
endothermic system.
Magnesium ions (Mg2+) is added to ensure a sharp endpoint during titration. Without them, a
premature endpoint may result.
Sodium hydroxide pellets are added to dispel turbidity (murkiness) in the solution. Excessive
addition may upset the pH balance of the solution and result in the formation of magnesium
hydroxide (Mg(OH)2).

NOTE: Calcium hydroxide (Ca(OH)2) will not precipitate because of its relatively high K sp value,
meaning it favors the ionic form.
Calcium Carbonate Solution (CaCO3)
NH3-NH4+ Buffer
The buffer is added to the solution to maintain a pH of 10. Ammonia was chosen because its
pKa value is approximately 9.26, very close to the desired value of 10. This is due to the
following reasons:
1) Sharp Endpoint
2) Increased Ca2+ and Mg2+ Selectivity
3) Wine Red to Blue Transition
Ammonia, due to its volatile nature, may evaporate if the solution is left uncovered. This will
result in a decrease in the pH value.

Excessive addition of the buffer may lead to a decrease in the sharpness of the endpoint.
SAMPLE ANALYSIS
As a hexadentate ligand, EDTA forms highly stable complexes with metal ions in the titration
process, which is one of the fundamental principles of the experiment. The Kf (Complex
Formation Constant) hierarchy is as follows,
Ca-EDTA > Mg-EDTA > MgIn- > CaIn-

More About Endpoint


Essentially, what happens at the endpoint is that all the MgIn - complexes are replaced with MgEDTA complexes, causing the shift to the blue indicator color.
Should a violet color change result, potassium cyanide (KCN) is added after the buffer to act as
a masking agent and prevent interference of iron.
HIn2- + Fe3+ -> FeIn- + H+
violet

6CN- + Fe3+ -> [Fe(CN)6]3This is possible because Kf of the Fe-CN complex is larger than that of the Fe-In complex.
Be warned, however, that although increasing the pH to 12 yields a sharper endpoint, the
formation of magnesium hydroxide (Mg(OH)2) is imminent and undesirable, causing much
error. OH- may result from the hydrolysis of the ammonia buffer in the solution.
CALCULATIONS
Molarity of EDTA Titrant
(

[EDTA] =
Remember that whatever you put for the aliquot factor has to make the numerator smaller
than the original since you diluted the solutions.
CaCO3 Titer
Titer =

Parts Per Million (PPM) CaCO3


ppm CaCO3 =

Experiment # 9
REDOX TITRATION: WINKLER METHOD FOR DISSOLVED OXYGEN DETERMINATION
INTRODUCTION
Primary Standard: Potassium Iodate (KIO3)
Titrant: Sodium Thiosulfate (Na2SO3)
Titrant/Analyte: Dissolved Oxygen
Indicator: 1% Starch Solution
Limiting Reactant: Dissolved Oxygen (O2)
The Winkler method is a redox titration method employed to test the life sustainability of pond
water. It makes use of several reduction-oxidation processes that relate the dissolved oxygen
content to the amount of titrant used. In this particular case, manganese (Mn2+) is both
reduced and oxidized at certain parts of the experiment.
STANDARDIZATION
Stoichiometric Ratio: 1 mmol IO3- = 6 mmols S2O32KIO3 is initially placed in the beaker, and water, potassium iodide (KI) and sulfuric acid (H 2SO4)
are eventually added to it in the order specified, yielding the following products in a dark
yellow solution.
IO3- + 8I- + 6H+ -> 3I3- + 3H2O
Sulfuric acid in particular was added due to the need for an acidic environment for the reaction
with iodate (IO3-) to take place.
The triiodide formed on the products side automatically decomposes according to the
following equation,
I3- -> I- + I2
The solution is then titrated with sodium thiosulfate until a pale yellow color is achieved. 1%
starch solution indicator is added, making the solution blue, and the solution is further titrated
until the colorless endpoint is achieved.
I2 + 2S2O32- -> 2I- + S4O62SAMPLE ANALYSIS
Stoichometric Ratio: 1 mmol O2 = 4 mmols S2O32-

A water sample filled to the brim in the bottle is opened and manganese sulfate (MnSO4),
ammonium hydrogen carbonate (NH4HCO3), and sodium hydroxide with potassium iodide
and azide (NaOH w/ KI w/ N3) are added to the solution in that specific order. The following
reactions proceed as a result.
Mn2+ + 2OH- -> Mn(OH)2
Mn(OH)2 + O2 + H2O -> Mn(OH)3 or 4MnO(OH)
The reason why there are two possible products for the second reaction is because scientists
have yet to confirm which of the two is formed.
Upon shaking the solution, a brown precipitate in the form of MnO(OH) 2 or Mn(OH)3 is formed,
and at this point, the oxygen content is fixed.
Concentrated phosphoric acid (H3PO4) is added and the bottle is shaken in order to dissolve the
brown precipitate. The following reaction proceeds,
6H+ + 2MnO(OH) + 2I- -> 2Mn2+ + I2 + 4H2O
Once completely dissolved, the solution is titrated with thiosulfate following the same
procedure as the standardization process.
EXPERIMENTAL CONCEPTS
Addition of Manganese Sulfate (MnSO4)
Manganese sulfate (MnSO4) is added in order to provide a steady source of Mn2+ ions for the
reaction to occur. Following this logic, it is also possible to make use of other sources of the ion,
such as manganese chloride (MnCl2). The important thing is to introduce manganese (II) ion to
the solution. Be wary though! Look back at the solubility rules for these compounds to make
sure they dissolve.
Addition of Ammonium Hydrogen Carbonate (NH4HCO3)
Ammonium hydrogen carbonate (NH4HCO3) is introduced to prevent the interference of
organic compounds in the solution. This is because organic compounds will gradually use up
the dissolved oxygen (O2).
Addition of Sodium Azide (NaN3)
The presence of Sodium azide (NaN3) serves to eliminate the interference of nitrite (NO 2-) in
the solution. This is because other than thiosulfate, nitrite will also be oxidized by iodine,
effectively reducing the volume of titrant used.
Addition of Sodium Carbonate (NaCO3)

Addition of this compound to the titrant stabilizes the sodium thiosulfate solution since it
decomposes in acidic environment according to the following reaction,
S2O32- + 2H+ -> SO2-(g) + S(s) + H2O
The carbonate is said to help reform sodium thiosulfate from the constituent products.
Addition of Phosphoric Acid (H3PO4)
Reason # 1: Acidic Environment for Redox Reaction
Explanation: The following equation shows the need for an acidic environment.
6H+ + 2MnO(OH) + 2I- -> 2Mn2+ + I2 + 4H2O
Reason # 2: Dissolution of Precipitate
Explanation: A pH value from 1 to 2.5 is needed in order to dissolve the MnO(OH) precipitate
into the solution.
Reason # 3: Inactivate Fe3+ Ions
Explanation: Ferric ions are reduced to ferrous ions, which can be accounted for and consume
0.14g of oxygen in according to the following reaction.
Fe2+ + O2- -> FeO
1% Starch Indicator
The need for freshly prepared starch is due to the hydrolysis that starch can undergo according
to the following reaction.
Starch -> Amylose + Amylopectin
Delay of starch addition, however, is in order to prevent the stabilization of the I2-starch
complex. The reason is that starch possesses a helical structure and once the I2 is introduced, it
is encaged within the helix. Should this happen, achieving the endpoint will be difficult.

Iodometry vs. Iodimetry

Redox Method
Titrant
Analyte

Iodometry
Sodium Thiosulfate
Iodine

Iodimetry
Iodine
Sodium Thiosulfate

The only real difference here is the choice of titrant and analyte.
CAUSE AND EFFECT
Addition of Sulfuric Acid before Potassium Iodide
Addition of sulfuric acid before potassium iodide will result into the formation of iodic acid
according to the following reaction.
IO3- + H+ -> HIO3
This causes the volume of thiosulfate to decrease, the molarity of thiosulfate to increase and
the calculated dissolved oxygen content to increase. This is because HIO3- is a weak acid,
meaning the dissociation into constituent ions is incomplete; thus, only some of the IO3- will be
titrated.
Lack of Shaking
Cause: After addition of NaOH, bottle was not shaken well.
Parameter: Dissolved Oxygen Concentration
Effect: Decrease
Explanation: Not all the dissolved oxygen is accounted for, possibly because not all of the
oxygen was precipitated into MnO(OH)
Cause: After addition of H3PO4, the bottle was not shaken well.
Parameter: Dissolved Oxygen Concentration
Effect: Decrease
Explanation: Similar to the previous question, not all of the dissolved oxygen is accounted for
because this time around not all the oxygen was dissolved.
No Boiled Distilled Water
Cause: Boiled distilled water was not used in standardization of sodium thiosulfate.
Parameter: Molarity of Sodium Thiosulfate
Effect: Decrease
Explanation: If the water isnt boiled, the formation of carbonic acid (H2CO3) is very possible.
Should this happen, this would provide a source of hydrogen ions for the following reaction to
occur.
S2O32-(g) + 2H+ -> S(s) + SO2- + H2O
This will cause the true concentration of S2O32- to decrease and the volume of titrant required
to increase.

Left Alone
Cause: Water sample without pre-treatment is left to stand overnight
Parameter: Dissolved Oxygen Content
Effect: Indeterminate
Explanation: The water sample may contain both heterotrophic and photosynthetic organisms
that will perform cellular respiration and photosynthesis. Effect on oxygen cannot be
ascertained.
Cause: Placed in locker
Parameter: Dissolved Oxygen Concentration
Effect: Decrease
Explanation: Dissolved oxygen will be consumed by heterotrophic organisms for respiration.
Cause: MnSO4 is added then left for an hour before KI w/ NaOH w/ Azide is added.
Parameter: Dissolved Oxygen Concentration
Effect: Decrease
Explanation: Manganese is light sensitive and thus undergoes reduction. This causes the
volume of titrant used to decrease and consequently the calculated dissolved oxygen
concentration to decrease too.
Additional Oxygen Sources
Cause: Partially filled sample bottle
Parameter: Dissolved Oxygen Concentration
Effect: Increase
Explanation: This is due to the additional oxygen that will dissolve coming from the air space
left behind.
Cause: Pipette is above water level
Parameter: Dissolved Oxygen Concentration
Effect: Increase
Explanation: Additional oxygen will be incorporated into the solution due to the distance
between the pipette and the water sample.
CALCULATIONS
Molarity of Sodium Thiosulfate Titrant
(

Remember that whatever you put for the aliquot factor has to make the numerator smaller
than the original since you diluted the solutions.

Parts Per Million (ppm) Dissolved Oxygen


(

ppm O2 =

Experiment # 10
DETERMINATION OF ELECTRODE POTENTIALS
INTRODUCTION
Electrode Cells: Copper, Zinc, Iron, Chlorine, Bromine and Iodine
Electrochemistry is a branch of chemistry which deals with the potentials of electrochemical
cells. These are made up of an electrode and a solution, and it is here where reductionoxidation reactions take place. The aim of the experiment is the measure the electric
potentials of individual galvanic and electrolytic cells.
The salt bridge is an important component of the set-up in order to maintain electro-neutrality.
One of the most important things to note is the relationship of the individual E cell values of the
solutions mentioned. The higher the Ecell value, the greater the ability to undergo reduction.
The reduction trend is as follows,
Cl > Br > I > Fe > Cu > Zn
This means that chlorine more readily undergoes reduction compared to the rest and is thus
the most powerful oxidizing agent. Zinc, on the other hand, more readily undergoes oxidation
and is the most powerful reducing agent.
Galvanic Cells versus Electrolytic Cells
Cell Type
Spontaneity
Cathode
Anode
Electron Flow
No. of Containers

GALVANIC CELL
Spontaneous
Positive
Negative
Anode to Cathode
Two

ELECTROLYTIC CELL
Nonspontaneous
Negative
Positive
Cathode to Anode
One

Electrodes Used
Half Cell
Zinc
Copper
Iron
Chlorine
Bromine
Iodine

Electrode
Zinc (Zn)
Copper (Cu)
Graphite (C)
Graphite (C)
Graphite (C)
Graphite (C)

The Electrolysis Part


Anode: Chloride, Bromide and Iodide ions
Reaction: 2Ha- -> Ha2 + 2e- (Ha = Halide)
Cathode: Water
Reaction: 2H2O + 2e- -> 2OH- + H2 (Efferevescence)
Here are the visible results in each cell once a current is passed through.
Chlorine: Effervescence is evident.
Bromine: Yellowish Coloration
Iodine: Yellowish Coloration
Water: Effervescence
CALCULATIONS
CASE 1: Standard-State Conditions (1M for solutions, 1 atm for gases, 25 C)
Ecell = Ecathode Eanode
CASE 2: Non-Standard Conditions
Ecell = Ecell
Ecell = Ecell

log Q
ln Q

Q here is the ratio of the concentration of products and reactants, each raised to their
respective coefficients.
CASE 3: Halide Group Enot Cell Calculations
This type of problem, most often than not, asks you to solve for either the Ecell or Ecell value of
the reaction. Thus, the following equation will be employed.
Ecell = Ecell

log

For this type of calculation, you will be needing the following essential parameters: current (A),
time(s), molarity of halide solution (M), volume of halide solution (mL).
1) [Ha-] =

Total Ha- moles =


( )

Unreacted Ha- moles =

2) [Ha2] =

( )

( )

( )

( )

*Number of electrons (n) and moles of electron (x) in the equation will be determined by the
reduction half-reaction.
Example: Cl2 + 2e- -> 2Cl- has n = 2 and x = 2 for its number and moles of electrons respectively.

Experiment # 11
POTENTIOMETRIC DETERMINATION OF THE PURITY AND DISSOCIATION CONSTANT OF
POTASSIUM HYDROGEN PHTHALATE
INTRODUCTION
Primary Standard: Potassium Hydrogen Phthalate (KHP)
Titrant: Sodium Hydroxide (NaOH)
Titrant/Analyte: Potassium Hydrogen Phthalate (KHP)
Indicator: None
Potentiometric titration is a widespread method employed in the titration of turbid solutions. It
is more efficient than indicator-based titrations due to the presence of a pH meter for accurate
quantitative measurement of the endpoint.
This method makes use of the original, first derivative and second derivative graphs to measure
the volume of titrant at equivalence point and pH at half-equivalence point (for pKa
measurement).
THE EXPERIMENTAL SET-UP
The set-up involves the following components: a magnetic stirrer, burette with titrant, and pH
meter and probe. This walkthrough will tackle the significance of each one at a time.
Magnetic Stirrer
The magnetic stirrer is employed in order to prevent disturbance of the system. This is because
with the burette and pH probe in place, manual stirring is almost impossible without hitting
either of the mentioned equipment.
Stirring is particularly important in order to disperse the titrant throughout the solution.
Imagine if there were no stirring mechanism. Wouldnt the titrant concentrate itself on the
surface of the solution? If the pH probe is within close proximity, it will read the pH of the
titrant instead of the pH of the overall solution, causing a drastic increase in the pH reading.
Sodium Hydroxide (NaOH) Titrant
Simply put, the potassium hydrogen phthalate (KHP) solution is acidic and thus must be titrated
with a basic titrant.

pH Probe

Storage
The pH probe is an essential and delicate tool in the potentiometric process, so it must be cared
for properly. It must be stored in an acidic solution with a pH of 3.
Why cant it be stored in distilled water, you ask? Recall that the glass probe contains a large
concentration of ions. The glass probe will be destroyed by the migration of ions from the
more concentrated area (glass probe) to the less concentrated area (distilled water). This
supply absolutely cannot be diminished else the pH probe will break.
Calibration
The calibration process of the pH meter involves the use of buffer solutions. These are freshly
prepared since they are organic compounds that easily decompose. They can be stored for a
maximum of one week before being thrown out.
First, the electrode should be rinsed with water then dipped in Buffer 7. Adjust the Slope
Knob until a reading of 7 is achieved. Rinse the electrode once more, but this time dip it in the
Buffer 4 solution. Turn the Buffer Knob until a reading of 4 pops up.
Limitation and Errors
Working pH Range: 0.5 12
Acid Error: pH < 0.5
Effect: The pH that flashes on the pH meter will be higher than the true pH.
Alkaline Error: pH > 12
Effect: pH that flashes on the pH meter will be lower than the true pH.
Parts of the Probe

The pH probe is made up of several components, two of which are significant to this discussion,
namely the indicator and reference electrodes.
REFERENCE ELECTRODE: AgCl/Ag
This is the wire that is found inside the pH meter probe. A general characteristic of the
reference electrode is that its Ecell value is independent of the concentration of ions in the
solution.
INDICATOR/ION-SELECTIVE ELECTRODE: Glass-Membrane Electrode
From the name itself, this electrode is selective towards the H+ ion, with its Ecell value
dependent on the ions concentration in the solution.
LIQUID PORTION OF PH PROBE: KCl
This part of the probe bridges the reference and indicator electrodes and acts as a supporting
electrolyte.
HOLE IN THE GLASS-ELECTRODE MEMBRANE
This connects the reference electrode to the surrounding solution.
GRAPHICAL ANALYSIS
These graphical trends are for the specific case of the experiment, where a weak acid was
titrated with a strong base. Graphs may vary for other combinations.

pH Reading

Original Graph

Volume of NaOH (mL)

The graph generally appears to be s-shaped, and the equivalence point can be found at the
inflection point of the graph.

First Derivative

First Derivative Graph

V' of Titrant (mL)

The graph generally appears to be hill-shaped, and the equivalence point can be found at the
absolute maximum point of the graph.

Second Derivative

Second Derivative Graph

V'' of Titrant (mL)

The graph appears to be lightning-shaped, and the equivalence point can be found at the xintercept of the graph.
For the graphs of diprotic and other polyprotic acids, the number of inflection points, relative
maxima and x-intercepts increase depending on how many times the acid can be
deprotonated (loss of H+).

The second row of graphs depicts the case of a weak base titrated with a strong acid.
Measuring pKa
pKa values can be easily determined by taking the Henderson-Hasselbalch equation.
pH = pKa + log
At half-equivalence point, it has been determined that the following relationship is true.
[A-] = [HA]
pH = pKa
ADVANTAGES OF POTENTIOMETRY OVER INDICATOR METHOD
Benefit # 1: Inexpensive
Explanation: The pH meter, although initially expensive, is a good investment since it can be
used for years after initial use and only requires occasional maintenance. On the other hand,
indicators must be purchased after stock depletion.
Benefit # 2: Accurate
Explanation: The exact numerical quantity of the endpoint can be determined through the pH
probe. Indicators, however, exhibit a color change over a pH range, which isnt very accurate.
Benefit # 3: Analysis of Turbid (Murky) Solutions
Explanation: Since a pH probe is being used, turbid solutions can be titrated and their endpoints
can still be determined. Indicators are not suitable in this case due to the possible color
interference from the turbid solutions.
CALCULATIONS
%Purity of KHP Sample
%Purity =

Experiment # 12
DETERMINATION OF COPPER (II) CONCENTRATION BY COLORIMETRIC METHOD
INTRODUCTION
Instrument: Single-Beam UV-VIS Spectrophotometer
Analyte: Copper (II) Solution
The colorimetric method deals specifically with the analysis of colors and their relationship
with other properties of the solution. In modern days, a spectrophotometer is used to gauge
significant quantities such as absorbance (A) and consequently concentration (M or ppm).
EXPERIMENTAL CONCEPTS
Parts of the Spectrophotometer

Always remember that the spectrophotometer is comprised of the light source, the
wavelength selector (monochromator), cuvette holder, detector and signal
processor/readout.
Transmittance
Transmittance (T) is the ratio of light transmitted through the solution (I) and the incident or
original light (Io). When light is fully transmitted, transmittance is one and absorbance is zero.
Conversely, when light is completely absorbed, transmittance is zero.
T=
Percent transmittance can be taken from transmittance using the following expression.
%T =

x 100%

The reason why transmittance is not used in graphical representation is because its relationship
with concentration is exponential.

Beers Law
Beer-Lamberts Law is an equation describing the relationship between absorbance (A) and
concentration (M or ppm). It shows that there is a linear relationship between the two and
that the equation is given by,
A = abc
a represents the absorptivity constant, which changes into or molar absorptivity when
concentration is in molarity (M). b, on the other hand, is the path length. It is important to note
that the units absorptivity (A) depend on the units of path length (b) and concentration (M or
ppm) since absorbance (A) has to be unitless.
Limitation of Beers Law
Real Limitation
For results to adhere to Beers Law, the concentration of solutions used should be dilute,
approximately less than 0.01 M. A higher concentration means molecules are in close proximity
with each other. The electrostatic interactions in these solutions cause a change in absorptivity
of the solution.
Chemical Limitation
Solutions must not undergo any kind of chemical reaction such as equilibration, dissociation,
precipitation, formation, etc. in the experimental process. This is because the color and
consequently the absorbance will change.
Instrumental Limitation

Factor # 1: Polychromatic Light

Polychromatic light or light with multiple wavelengths will cause a deviation from linearity
described by the image above. As E1 increases and E2 decreases, the graph appears to bend
forward.
Factor # 2: Stray Light
There is always a decrease in the absorbance value when stray light is introduced. The
numerical determination of this error is given by the following equation.
A = -log
Ps is the quantification of stray light.
Factor # 3: Mismatched Cell

An integral part of the experiment is the use of standardized equipment, particularly of


cuvettes. The cuvette used in the auto-zero phase should also be employed for the analysis
part.
Absorbance increases due to the longer path length that needs to be traversed by the light.
The plot then deviates from linearity.
The Concept Behind Auto-Zero
Auto-zero is performed in order to eliminate the effects of quantities that we do not wish to be
part of the absorbance (A) reading. In particular, this means negating the effects of the
scattering, reflecting and refracting of light by the cuvette and the absorbance of the
ammonia solution.
This means that neglecting to perform the auto-zero phase results in an increased absorbance
reading.

Significance of Lambda Max


Ideal Lambda Max: 615 nanometers
Reason # 1: Absorbance per Unit Concentration
Explanation: The change in absorbance per unit concentration is greatest at this point. This
means that the calibration curve becomes much wider and can accommodate a large working
range. There is then a higher probability that the absorbance of the sample is within the
calibration curve.
Reason # 2: Increased Sensitivity
Explanation: Even if the concentration of the sample is small, the instrument is still able to
detect it efficiently.
Reason # 3: Linear Relationship of A and c
Explanation: At lambda max, A and c exhibit a linear relationship. At any other point, there is
deviation from linearity.
Complementary Color

It is vital that one remembers the concept of complementary color. The color wheel can be
made a reference for this. Basically, the wavelength that is absorbed by the solution is the
complement of the wavelength that is transmitted and received by our eyes.
For example, if the solution transmits a blue color to our eyes, it means that the orange
wavelength is being absorbed.

The Calibration Curve

A number of things should be considered in the construction of the calibration curve. Note first
that the blank solution is not included in the graph. Concentration and absorbance values of
the standard solutions are plotted and a line (trendline) is taken. The sample solutions
concentration is then determined from the slope of the graph and related using the following
algebraic equation,
y = mx + b
Here, y represents the absorbance (A) of the sample solution. X is then determined by isolating
the variable. If the absorbance of the sample solution is higher than the absorbance value of
the most concentrated standard, the student may dilute the solution. However, if the
absorbance of the sample solution is lower than that of the least concentrated solution, a less
concentrated standard should be made and its data should be added to the graph.
Solution Preparation
Ammonia is added to the solution in order to forward the following reaction,
Cu2+ + 4NH3 -> [Cu(NH3)4]2+
The copper-ammonia complex formed has a more intense color than the copper solution,
allowing it to be examined effectively by the spectrophotometer.
If there is only a limited amount of ammonia, the hydrolysis of ammonia may proceed and
cause the formation of copper hydroxide.
NH3 + H2O <-> NH4+ + OHCu2+ + OH- <-> Cu(OH)2

Experiment # 13
DETERMINATION OF TOTAL ION CONCENTRATION USING ION-EXCHANGE CHROMATOGRAPHY
INTRODUCTION
Mobile Phase: Distilled Water (H2O)
Stationary Phase: Cation-Exchange Resin (Dowex 50)
Analyte: Copper (II) Solution
Ion-exchange chromatography is a method founded on the concept of ion exchange between
two principle sites, the mobile phase and the stationary phase. The stationary phase used in
the experiment is a resin. An unknown solution is passed through the resin, where the ion
replaces H+/OH- ions that are bound to the binding sites. Measurement is done by titrating the
solution (or eluate) that is collected in a beaker at the base of the set-up.
The exchange process in the experiment is described by the following reaction.
nRSO3-H+ + Mn+ -> (RSO3)nM + nH+
THE EXPERIMENTAL SET-UP
The Resin
This is the stationary phase of the set-up. There are generally two types of resins, the cationexchange (CATEX) resin and the anion-exchange (ANEX) resin. As the name states, a CATEX is
used for the analysis of cations, while an ANEX is used for the analysis of anions. The following
table lists examples of commercially available resins.

Functional Group
Resin Name
Functional Group
ANEX Strength
pH Range

Anion-Exchange Resins (ANEX)


Basic (OH-) Functional Group
Amberlite IR 410
Dowex 2
-NH4+-OH
N(CH3)-3OH
Strong
Weak
0 - 12
09

Functional Group
Resin Name
Functional Group
CATEX Strength
pH Range

Cation-Exchange Resins (CATEX)


Acidic (H+) Functional Group
Amberlite IR 400
-COO-H+
Weak
5 - 14

Dowex 50
SO3-H+
Strong
1-14

In the experiment, Dowex 50 was picked as the stationary phase in the analysis of Cu 2+ ions.
The pH of the environment was not adjusted anymore due to the large functional pH range
possessed by the resin.
EXPERIMENTAL CONCEPTS
Exchange Capacity
The exchange capacity of a resin is given by the following equation.
Exchange Capacity =
What this means is that the large the exchange capacity, the more exchange sites the resin has.
For CATEX resins, H+ is used, while with ANEX resins, H + is replaced with OH- in the equation.
Exchange Factors
There are a number of factors affecting the efficiency of exchange between the solution and
the resin. This is usually measured using the time of elution (time it takes for the ion to reach
the beaker) and is governed by two factors.
Factor # 1: Ionic Charge
Explanation: The larger the charge of the ion being analyzed, the greater its affinity for the
resin. This means that compared to other ions of lower charge, an ion of higher charge will take
longer to reach the beaker due to its attraction for the resin.
Example: Aluminum (Al3+), Barium (Ba2+), Potassium (K+)
Parameter: Time of Elution
Al3+ > Ba2+ > K+
K+ < Ba2+ < Al3+

(Decreasing Time of Elution)


(Increasing Time of Elution)

This just means that K+ will be the first to be eluted (reach the beaker) due to its relatively
small charge, while Al3+ will be the last.
Factor # 2: Size
Explanation: The larger the size of the ion, the greater the affinity of the ion for the resin.
Recall that the overall trend for atomic size increases when moving to the left and down of the
periodic table. It is important to note that Francium (Fr+) is then the largest element in the
table.
Example: Potassium (K+), Sodium (Na+), Cesium (Ce+)
Parameter: Time of Elution

Ce+ > Na+ > K+


K+ < Na+ < Ce+

(Decreasing Time of Elution)


(Increasing Time of Elution)

This just means that K+ will be the first to be eluted (reach the beaker) due to its relatively
small size, while Ce+ will be the last.
In a combination problem, first priority is given to the charge of the ion. Once charge has been
factored in, size then comes into play.
Example: Aluminum (Al3+), Calcium (Ca2+), Potassium (K+), Cesium (Ce+), Sulfate (SO3-)
Additional Condition: Assume that this is a CATEX resin.
Parameter: Time of Elution
Al3+ > Ca2+ > Ce+ > K+ > SO3- (Decreasing Time of Elution)
SO3- < K+ < Ce+ < Ca2+ < Al3+ (Increasing Time of Elution)
Note that SO3- has the smallest time of elution since we are using a CATEX and it is an anion,
meaning it simply passes through the resin. Moreover, note that Ce+ is larger than K+ and thus
takes significant longer to be eluted.
Factor # 3: Concentration
At the end of the experiment, the copper (II) ions were washed out of the resin using 6.0 M HCl.
How is this possible when copper (II) ions with a charge of +2 have a greater affinity than
hydrogen ions of charge +1?
The answer lies in the fact that 6.0M was used to wash the resin. This concentration is
significantly larger than the copper (II) solution, and this allowed the H+ to replace the copper
(II) ions bound to the exchange sites.
Factor # 4: Cross-Linking of the Resin Polymer
Resin is known to be composed of styrene polymers. In order for polymers to be formed from
monomers, cross-linking must occur.
The problem here is that a high degree of cross-linking translates to less pores and thus less
exchange sites. Conversely, a low degree of cross-linking translates to more pores and more
exchange sites.

Factor # 5: Power of Hydrogen (pH)

Example: Amino Acid


Basic pH: Amino acid becomes an anion.
Acidic pH: Amino acid becomes a cation.
Factor # 6: 15 Drops/Minute Flow Rate
This is done in order to ensure that all the copper (II) ions bind to the exchange sites in the
resin. If the rate is too fast, an incomplete exchange process will result and less Cu2+ will bind to
the sites. If it is too slow, however, the process is deemed inefficient due to the increased
amount of time needed to complete the procedure.
METHODOLOGY
Resin Soaked in Water

This is done to dissolve water-soluble impurities and to ionize the functional groups of the
resin. Water-soluble impurities are troublesome because they can block off access to exchange
sites. Through immersion in water, the resin was also allowed to swell, causing exposure of
exchange sites.

Resin Soaked in Acid


This is done in order to replace any bound ions in the resin and replenish the hydrogen ion (H +)
supply.
Maintenance of Above-Resin Water Level

This is in order to prevent the formation of air pockets, which may restrict access of the ions to
the binding sites. These air pockets will decrease the number of available binding sites and the
amount of ions bound to them.
pH Equality of H2O and Eluate
Elution Phase
Cause: pH equality is not satisfied
Parameter: Cu2+ Concentration
Effect: Increase
Explanation: The calculated Cu 2+ concentration will increase because excess H+ coming from the
excess acid (poured to replenish H+) will be added to the eluate and subsequently analyzed.
Calculations will lead to a higher resultant Cu2+ from a higher H+ concentration.
Titration Phase
Cause: pH equality is not satisfied
Parameter: Cu2+ Concentration
Effect: Decrease
Explanation: Cu2+ concentration will decrease because if the pH is not equal, that signifies that
not all of the Cu2+ was able to bind with the resin and not all of the H+ is present in the eluate.

CALCULATIONS
Molarity of Cu2+ in Unknown Sample
[Cu2+] =