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Chemistry 26.

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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. EDTA forms highly stable complexes with metal ions in the titration process. This is due to the following reasons: 1) Sharp Endpoint 2) Increased Ca2+ and Mg2+ Selectivity 3) Wine Red to Blue Transition Ammonia. Ammonia was chosen because its pKa value is approximately 9. meaning it favors the ionic form. may evaporate if the solution is left uncovered. very close to the desired value of 10.> CaIn- . Excessive addition of the buffer may lead to a decrease in the sharpness of the endpoint. due to its volatile nature. which is one of the fundamental principles of the experiment. The Kf (Complex Formation Constant) hierarchy is as follows. Ca-EDTA > Mg-EDTA > MgIn. This will result in a decrease in the pH value.26. SAMPLE ANALYSIS As a hexadentate ligand. Calcium Carbonate Solution (CaCO3) NH3-NH4+ Buffer The buffer is added to the solution to maintain a pH of 10.

Be warned.More About Endpoint Essentially.+ H+ violet 6CN. causing much error. causing the shift to the blue indicator color. however. CaCO3 Titer Titer = ( ) Parts Per Million (PPM) CaCO3 ppm CaCO3 = ( ) .may result from the hydrolysis of the ammonia buffer in the solution.+ Fe3+ -> [Fe(CN)6]3This is possible because Kf of the Fe-CN complex is larger than that of the Fe-In complex. 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.complexes are replaced with MgEDTA complexes. 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.+ Fe3+ -> FeIn. that although increasing the pH to 12 yields a sharper endpoint. HIn2. OH. what happens at the endpoint is that all the MgIn . the formation of magnesium hydroxide (Mg(OH)2) is imminent and undesirable.

+ 6H+ -> 3I3. It makes use of several reduction-oxidation processes that relate the dissolved oxygen content to the amount of titrant used. making the solution blue. 1% starch solution indicator is added. manganese (Mn2+) is both reduced and oxidized at certain parts of the experiment. and the solution is further titrated until the colorless endpoint is achieved. STANDARDIZATION Stoichiometric Ratio: 1 mmol IO3. I2 + 2S2O32.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.+ I2 The solution is then titrated with sodium thiosulfate until a pale yellow color is achieved. In this particular case. I3. IO3.= 6 mmols S2O32KIO3 is initially placed in the beaker.+ 3H2O Sulfuric acid in particular was added due to the need for an acidic environment for the reaction with iodate (IO3-) to take place. and water. potassium iodide (KI) and sulfuric acid (H 2SO4) are eventually added to it in the order specified.-> I.-> 2I. yielding the following products in a dark yellow solution. The triiodide formed on the products’ side automatically decomposes according to the following equation.+ 8I.+ S4O62SAMPLE ANALYSIS Stoichometric Ratio: 1 mmol O2 = 4 mmols S2O32- .

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

Fe2+ + O2. is in order to prevent the stabilization of the I2-starch complex. it is “encaged” within the helix. which can be accounted for and consume 0.Addition of this compound to the titrant stabilizes the sodium thiosulfate solution since it decomposes in acidic environment according to the following reaction. Reason # 3: Inactivate Fe3+ Ions Explanation: Ferric ions are reduced to ferrous ions. Should this happen. S2O32. Iodimetry Redox Method Titrant Analyte Iodometry Sodium Thiosulfate Iodine Iodimetry Iodine Sodium Thiosulfate . The reason is that starch possesses a helical structure and once the I2 is introduced. Iodometry vs. 6H+ + 2MnO(OH) + 2I. Addition of Phosphoric Acid (H3PO4) Reason # 1: Acidic Environment for Redox Reaction Explanation: The following equation shows the need for an acidic environment. Starch -> Amylose + Amylopectin Delay of starch addition. however.-> 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.14g of oxygen in according to the following reaction.-> FeO 1% Starch Indicator The need for freshly prepared starch is due to the hydrolysis that starch can undergo according to the following reaction. achieving the endpoint will be difficult.+ 2H+ -> SO2-(g) + S(s) + H2O The carbonate is said to help reform sodium thiosulfate from the constituent products.

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

Parameter: Dissolved Oxygen Concentration Effect: Decrease Explanation: Manganese is light sensitive and thus undergoes reduction. . 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. This causes the volume of titrant used to decrease and consequently the calculated dissolved oxygen concentration to decrease too. 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.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: MnSO4 is added then left for an hour before KI w/ NaOH w/ Azide is added. Cause: Placed in locker Parameter: Dissolved Oxygen Concentration Effect: Decrease Explanation: Dissolved oxygen will be consumed by heterotrophic organisms for respiration. 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.

Parts Per Million (ppm) Dissolved Oxygen ( ppm O2 = ) .

Zinc. The reduction trend is as follows. Zinc. and it is here where reductionoxidation reactions take place. Bromine and Iodine Electrochemistry is a branch of chemistry which deals with the potentials of electrochemical cells. The higher the E⁰cell value. the greater the ability to undergo reduction. 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. Galvanic Cells versus Electrolytic Cells Cell Type Spontaneity Cathode Anode Electron Flow No. The aim of the experiment is the measure the electric potentials of individual galvanic and electrolytic cells. Chlorine. These are made up of an electrode and a solution. One of the most important things to note is the relationship of the individual E cell values of the solutions mentioned. Iron. 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) . on the other hand. more readily undergoes oxidation and is the most powerful reducing agent. The salt bridge is an important component of the set-up in order to maintain electro-neutrality.Experiment # 10 DETERMINATION OF ELECTRODE POTENTIALS INTRODUCTION Electrode Cells: Copper.

-> Ha2 + 2e.-> 2OH. Thus. Chlorine: Effervescence is evident. volume of halide solution (mL).(Ha = Halide) Cathode: Water Reaction: 2H2O + 2e. you will be needing the following essential parameters: current (A). each raised to their respective coefficients. time(s).+ H2 (Efferevescence) Here are the visible results in each cell once a current is passed through. 1) [Ha-] = – .The Electrolysis Part Anode: Chloride. Bromide and Iodide ions Reaction: 2Ha. Bromine: Yellowish Coloration Iodine: Yellowish Coloration Water: Effervescence CALCULATIONS CASE 1: Standard-State Conditions (1M for solutions. most often than not. molarity of halide solution (M). 25⁰ C) E⁰cell = Ecathode – Eanode CASE 2: Non-Standard Conditions Ecell = E⁰cell – Ecell = E⁰cell – log Q ln Q Q here is the ratio of the concentration of products and reactants. the following equation will be employed. Ecell = E⁰cell – log For this type of calculation. asks you to solve for either the Ecell or E⁰cell value of the reaction. 1 atm for gases. CASE 3: Halide Group Enot Cell Calculations This type of problem.

.moles = ( ) Unreacted Ha.has n = 2 and x = 2 for its number and moles of electrons respectively.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.( Total Ha.

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. This walkthrough will tackle the significance of each one at a time. It is more efficient than indicator-based titrations due to the presence of a pH meter for accurate quantitative measurement of the endpoint. Imagine if there were no stirring mechanism. it will read the pH of the titrant instead of the pH of the overall solution. Wouldn’t the titrant concentrate itself on the surface of the solution? If the pH probe is within close proximity. burette with titrant. causing a drastic increase in the pH reading.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. first derivative and second derivative graphs to measure the volume of titrant at equivalence point and pH at half-equivalence point (for pKa measurement). and pH meter and probe. . THE EXPERIMENTAL SET-UP The set-up involves the following components: a magnetic stirrer. Sodium Hydroxide (NaOH) Titrant Simply put. the potassium hydrogen phthalate (KHP) solution is acidic and thus must be titrated with a basic titrant. Magnetic Stirrer The magnetic stirrer is employed in order to prevent disturbance of the system. This method makes use of the original.

so it must be cared for properly. Calibration The calibration process of the pH meter involves the use of buffer solutions. the electrode should be rinsed with water then dipped in Buffer 7. First. Limitation and Errors Working pH Range: 0. but this time dip it in the Buffer 4 solution. This supply absolutely cannot be diminished else the pH probe will break.5 Effect: The pH that flashes on the pH meter will be higher than the true pH. Rinse the electrode once more. Parts of the Probe . 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). Alkaline Error: pH > 12 Effect: pH that flashes on the pH meter will be lower than the true pH. These are freshly prepared since they are organic compounds that easily decompose. Why can’t it be stored in distilled water. Adjust the “Slope Knob” until a reading of 7 is achieved.5 – 12 Acid Error: pH < 0.pH Probe Storage The pH probe is an essential and delicate tool in the potentiometric process. They can be stored for a maximum of one week before being thrown out. Turn the “Buffer Knob” until a reading of 4 pops up. you ask? Recall that the glass probe contains a large concentration of ions. It must be stored in an acidic solution with a pH of 3.

pH Reading Original Graph Volume of NaOH (mL) The graph generally appears to be s-shaped. A general characteristic of the reference electrode is that its Ecell value is independent of the concentration of ions in the solution. this electrode is selective towards the H+ ion. with its Ecell value dependent on the ion’s 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. INDICATOR/ION-SELECTIVE ELECTRODE: Glass-Membrane Electrode From the name itself. and the equivalence point can be found at the inflection point of the graph. where a weak acid was titrated with a strong base. Graphs may vary for other combinations. namely the indicator and reference electrodes. GRAPHICAL ANALYSIS These graphical trends are for the specific case of the experiment. REFERENCE ELECTRODE: AgCl/Ag This is the wire that is found inside the pH meter probe.The pH probe is made up of several components. two of which are significant to this discussion. . HOLE IN THE GLASS-ELECTRODE MEMBRANE This connects the reference electrode to the surrounding solution.

First Derivative First Derivative Graph V' of Titrant (mL) The graph generally appears to be hill-shaped. For the graphs of diprotic and other polyprotic acids. relative maxima and x-intercepts increase depending on how many times the acid can be deprotonated (loss of H+). the number of inflection points. and the equivalence point can be found at the xintercept of the graph. . 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.

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

When light is fully transmitted.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. transmittance is zero. detector and signal processor/readout. Conversely. %T = x 100% The reason why transmittance is not used in graphical representation is because its relationship with concentration is exponential. EXPERIMENTAL CONCEPTS Parts of the Spectrophotometer Always remember that the spectrophotometer is comprised of the light source. cuvette holder. transmittance is one and absorbance is zero. In modern days. T= Percent transmittance can be taken from transmittance using the following expression. . a spectrophotometer is used to gauge significant quantities such as absorbance (A) and consequently concentration (M or ppm). Transmittance Transmittance (T) is the ratio of light transmitted through the solution (I) and the incident or original light (Io). when light is completely absorbed. the wavelength selector (monochromator).

which changes into ε or molar absorptivity when concentration is in molarity (M). 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. Chemical Limitation Solutions must not undergo any kind of chemical reaction such as equilibration. approximately less than 0. The electrostatic interactions in these solutions cause a change in absorptivity of the solution. It shows that there is a linear relationship between the two and that the equation is given by. the concentration of solutions used should be dilute. Limitation of Beer’s Law Real Limitation For results to adhere to Beer’s Law. etc. is the path length. Instrumental Limitation Factor # 1: Polychromatic Light .01 M. in the experimental process. on the other hand. A = abc a represents the absorptivity constant. This is because the color and consequently the absorbance will change. precipitation. dissociation. A higher concentration means molecules are in close proximity with each other.Beer’s Law Beer-Lambert’s Law is an equation describing the relationship between absorbance (A) and concentration (M or ppm). b. formation.

This means that neglecting to perform the auto-zero phase results in an increased absorbance reading. As E1 increases and E2 decreases. Factor # 3: Mismatched Cell An integral part of the experiment is the use of standardized equipment. In particular. Factor # 2: Stray Light There is always a decrease in the absorbance value when stray light is introduced. the graph appears to bend forward. . Absorbance increases due to the longer path length that needs to be traversed by the light. 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. The cuvette used in the auto-zero phase should also be employed for the analysis part. this means negating the effects of the scattering.Polychromatic light or light with multiple wavelengths will cause a deviation from linearity described by the image above. reflecting and refracting of light by the cuvette and the absorbance of the ammonia solution. A = -log Ps is the quantification of stray light. The plot then deviates from linearity. particularly of cuvettes. The numerical determination of this error is given by the following equation.

This means that the calibration curve becomes much wider and can accommodate a large working range. it means that the orange wavelength is being absorbed. if the solution transmits a blue color to our eyes. For example. Reason # 2: Increased Sensitivity Explanation: Even if the concentration of the sample is small. The color wheel can be made a reference for this. the instrument is still able to detect it efficiently. Basically. There is then a higher probability that the absorbance of the sample is within the calibration curve. the wavelength that is absorbed by the solution is the complement of the wavelength that is transmitted and received by our eyes. At any other point.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. Complementary Color It is vital that one remembers the concept of complementary color. there is deviation from linearity. . Reason # 3: Linear Relationship of A and c Explanation: At lambda max. A and c exhibit a linear relationship.

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

the cationexchange (CATEX) resin and the anion-exchange (ANEX) resin. nRSO3-H+ + Mn+ -> (RSO3)nM + nH+ THE EXPERIMENTAL SET-UP The Resin This is the stationary phase of the set-up. while an ANEX is used for the analysis of anions. a CATEX is used for the analysis of cations. the mobile phase and the stationary phase.ions that are bound to the binding sites. There are generally two types of resins. As the name states. The following table lists examples of commercially available resins. The stationary phase used in the experiment is a resin. 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 . The exchange process in the experiment is described by the following reaction.14 Dowex 50 SO3-H+ Strong 1-14 . where the ion replaces H+/OH.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. Measurement is done by titrating the solution (or eluate) that is collected in a beaker at the base of the set-up.12 0–9 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 . An unknown solution is passed through the resin.

For CATEX resins. the greater its affinity for the resin. Cesium (Ce+) Parameter: Time of Elution . Dowex 50 was picked as the stationary phase in the analysis of Cu 2+ ions. Factor # 1: Ionic Charge Explanation: The larger the charge of the ion being analyzed.in the equation. the more exchange sites the resin has. H + is replaced with OH. The pH of the environment was not adjusted anymore due to the large functional pH range possessed by the resin. 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. Exchange Factors There are a number of factors affecting the efficiency of exchange between the solution and the resin. Recall that the overall trend for atomic size increases when moving to the left and down of the periodic table. while Al3+ will be the last.In the experiment. Example: Potassium (K+). Barium (Ba2+). H+ is used. the greater the affinity of the ion for the resin. while with ANEX resins. This means that compared to other ions of lower charge. EXPERIMENTAL CONCEPTS Exchange Capacity The exchange capacity of a resin is given by the following equation. Sodium (Na+). It is important to note that Francium (Fr+) is then the largest element in the table. 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. Exchange Capacity = What this means is that the large the exchange capacity. Example: Aluminum (Al3+). Factor # 2: Size Explanation: The larger the size of the ion. an ion of higher charge will take longer to reach the beaker due to its attraction for the resin.

Calcium (Ca2+).< K+ < Ce+ < Ca2+ < Al3+ (Increasing Time of Elution) Note that SO3. Moreover. Factor # 3: Concentration At the end of the experiment. cross-linking must occur. Example: Aluminum (Al3+). and this allowed the H+ to replace the copper (II) ions bound to the exchange sites. 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. Conversely. This concentration is significantly larger than the copper (II) solution.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. Sulfate (SO3-) Additional Condition: Assume that this is a CATEX resin. Parameter: Time of Elution Al3+ > Ca2+ > Ce+ > K+ > SO3. The problem here is that a high degree of cross-linking translates to less pores and thus less exchange sites. Cesium (Ce+).0 M HCl. Factor # 4: Cross-Linking of the Resin Polymer Resin is known to be composed of styrene polymers.has the smallest time of elution since we are using a CATEX and it is an anion. In order for polymers to be formed from monomers. Once charge has been factored in.0M was used to wash the resin. Potassium (K+). the copper (II) ions were washed out of the resin using 6. first priority is given to the charge of the ion. while Ce+ will be the last. size then comes into play. note that Ce+ is larger than K+ and thus takes significant longer to be eluted. In a combination problem. a low degree of cross-linking translates to more pores and more exchange sites. .(Decreasing Time of Elution) SO3. meaning it simply passes through the resin.

Through immersion in water. If it is too slow. causing exposure of exchange sites. If the rate is too fast. the resin was also allowed to swell. an incomplete exchange process will result and less Cu2+ will bind to the sites. however. Water-soluble impurities are troublesome because they can block off access to exchange sites. Acidic pH: Amino acid becomes a cation. 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. 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.Factor # 5: Power of Hydrogen (pH) Example: Amino Acid Basic pH: Amino acid becomes an anion. .

Resin Soaked in Acid This is done in order to replace any bound ions in the resin and replenish the hydrogen ion (H +) supply. which may restrict access of the ions to the binding sites. Calculations will lead to a higher resultant Cu2+ from a higher H+ concentration. Maintenance of Above-Resin Water Level This is in order to prevent the formation of air pockets. 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. 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. . These air pockets will decrease the number of available binding sites and the amount of ions bound to them. 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+] = ( ) .