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Chemistry 26-1-2nd Laboratory Examination Reviewer
Chemistry 26-1-2nd Laboratory Examination Reviewer
1
nd
2 Written Laboratory Examination Reviewer
A.Y. 2010 – 2011
Experiment # 8
QUANTITATIVE DETERMINATION OF TOTAL HARDNESS IN DRINKING WATER BY
COMPLEXOMETRIC EDTA TITRATION
INTRODUCTION
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.
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.
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.
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)
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.
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
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,
Essentially, what happens at the endpoint is that all the MgIn - complexes are replaced with Mg-
EDTA 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.
This 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
( )
[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 = ( )
( )
ppm CaCO3 =
Experiment # 9
REDOX TITRATION: WINKLER METHOD FOR DISSOLVED OXYGEN DETERMINATION
INTRODUCTION
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
KIO3 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.
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.
SAMPLE ANALYSIS
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,
Once completely dissolved, the solution is titrated with thiosulfate following the same
procedure as the standardization process.
EXPERIMENTAL CONCEPTS
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.
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,
The carbonate is said to help reform sodium thiosulfate from the constituent products.
1% Starch Indicator
The need for freshly prepared starch is due to the hydrolysis that starch can undergo according
to the following reaction.
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.
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 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.
Cause: Boiled distilled water was not used in standardization of sodium thiosulfate.
Parameter: Molarity of Sodium Thiosulfate
Effect: Decrease
Explanation: If the water isn’t 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.
This will cause the true concentration of S2O32- to decrease and the volume of titrant required
to increase.
Left Alone
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.
CALCULATIONS
( )
[ =
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
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 E⁰cell value, the greater the ability to undergo reduction.
The reduction trend is as follows,
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.
Electrodes Used
Cathode: Water
Reaction: 2H2O + 2e- -> 2OH- + H2 (Efferevescence)
Here are the visible results in each cell once a current is passed through.
CALCULATIONS
CASE 1: Standard-State Conditions (1M for solutions, 1 atm for gases, 25⁰ C)
Q here is the ratio of the concentration of products and reactants, each raised to their
respective coefficients.
This type of problem, most often than not, asks you to solve for either the Ecell or E⁰cell value of
the reaction. Thus, the following equation will be employed.
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 = ( ) ( )
( ) ( )
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
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 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. Wouldn’t 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.
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 can’t 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.
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.
From the name itself, this electrode is selective towards the H+ ion, with its Ecell value
dependent on the ion’s concentration in the solution.
This part of the probe bridges the reference and indicator electrodes and acts as a supporting
electrolyte.
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.
Original Graph
pH Reading
The graph generally appears to be s-shaped, and the equivalence point can be found at the
inflection point of the graph.
First Derivative Graph
First Derivative
The graph generally appears to be hill-shaped, and the equivalence point can be found at the
absolute maximum point of the graph.
The graph appears to be lightning-shaped, and the equivalence point can be found at the x-
intercept 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
pH = pKa + log
At half-equivalence point, it has been determined that the following relationship is true.
[A-] = [HA]
pH = pKa
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 isn’t very accurate.
CALCULATIONS
( )
%Purity =
Experiment # 12
DETERMINATION OF COPPER (II) CONCENTRATION BY COLORIMETRIC METHOD
INTRODUCTION
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
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.
Beer’s Law
Beer-Lambert’s 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 ε 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.
Real Limitation
For results to adhere to Beer’s 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
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
Absorbance increases due to the longer path length that needs to be traversed by the light.
The plot then deviates from linearity.
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
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 solution’s
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
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.
INTRODUCTION
The Resin
This is the stationary phase of the set-up. There are generally two types of resins, the cation-
exchange (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.
EXPERIMENTAL CONCEPTS
Exchange Capacity
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.
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.
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.
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)
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
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.
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.
Elution Phase
Titration Phase
( )
[Cu2+] =