ae: Thermodynamics of Cobalt Complexation Objectives 1 ‘To explore the thermodynamics of a complexation equilibrium between two Co complexes by fot” lowing the equilibridm absorbantce’oF one ofthe complexes..a function ofthe temperature. From the absorbance of ane component in af &t a the concentrations of all componenis as well as the equilibrium constant can be derived. The equilibrium constant at each given tempera- ture determines the value of Gibb’s free energy, AG’. When AG" is plotted vs. the absolute tempera- ture, AH? and AS” can be calculated from the intercept and the slope of the straight line obtained. mys Introduction ) “This experiment studies the complexation reactions of the cobalt(I) ion. When present in an aque-( ous solution, the Co? ion is never actually present by itself water molecules surround it to form a so-called “complex ion” with the formula [Co(H,0),}"*. These coordinated water molecules are called ligands. (Formulas for complex ions are always written using the square brackets. These complex ions don’t always carry overall charge but they still are complex ions in their nature be- ‘cause of the type of bonding between the central ion and the ligands surrounding it.) As.a result of this complexation, when a cobale sal, such as CoCl, is dissolved in water and then recrystallized, the hydrated form of the cobalt salt—in this case, CoCl, . 6H,O—is obtained. This hydrated salt can be re-dissolved in an excess of a certain solvent, such as ethanol (henceforth abbreviated as E:OH), to displace all of the water ligands and obtain a new coordinate complex. However, the number of ligands in this new complex surrounding the central cobalt ion does not necessarily 1m(Chemistry122 Laboratory Manual | Dr. Annamaria Flep have to be the same as the original, especially at different temperatures. This is the case in the system studied in this experiment. We are looking at a complexation equilibrium that involves a change in the numbet of ligands in the coordinate complex, and thus an alteration in the geometry of the complex ‘as well. This change in geometry causes an observable change in the color of the solution, providing us with conditions that can be monitored by visible-light spectroscopy. ‘We will be studying the complexation of cobalt(II) chloride (obtained from its hexahydrate form) in ‘ethanol. The equilibrium of this system can be represented as 7 [Co(EtOH),(Cl)q] = [Co(E:OH),(C),] + 2EOH Notice that the cobalt complex on the left side of the reaction, [Co(EtOH)4(Cl)2], has six ligands surrounding the central cobalt ion, indicating an octahedral geometry. The cobalt complex on the right, [Co(EtOH),(Cl)2], has four ligands, indicating a tetrahedral geometry. Since the tetrahedral [Co(EOH),(Cl)2} complex absorbs light the strongest at 655 nm, the concentration of this tetrahedral complex can be monitored by measuring its light absorbance. ‘The Beer-Lambert equation can then be used to calculate the concentration of the product tetrahedral cobalt species at different temperatures. Ieis then also possible to calculate the equilibrium concentrations of the octahedral cobalt species and the ethanol from the known total concentrations of cobalt and ethanol at those temperatures. The Equilibti mi €onstant,and GibWis:Free Energy . ee s eee 2 Recall chat the equilibrium constant for any reaction can be calculated from the concentrations of the components (dissolved or gaseous) of the reaction at equilibrium. For a generic reaction: aA(aq) + bB(ag) => cC(aq) + dD(aq) . (eq 1) where A and B are reactants, C and D ate products, and a, b, cand d are their coefficients, the equilib- rium constant of the reaction can be expressed as . {cI (or = [ayy "(a2 The value of the equilibrium constant varies with the temperature of the reaction. The standard free energy change of the reaction and K,, are also related; the equilibrium constant becomes larger as the standard free energy change becomes more negative. AG? =-RT In K, (eq3) where AG" represents Gibbs free energy at the given temperature, Tis the absolute temperature and R is the gas constant, The temperature value in equation 3 must be in Kelvin. ‘The unie for AG? will be n | 1 i ‘ ( ( ( ( 4 “4 ( ( ‘ ( Sahn eennewence‘Thermodynamics of Cobalt Complexation Jmol if we use the value for R equal to 8.3145 a ‘The Gibbs energy essentially indicates whether : a reaction will happen spontaneously ata given temperature. Relating AG’ to Entropy and Enthalpy ; AG? can also be related to the standard enthalpy (AH*) and entropy (AS*) values for a feaction. En- thalpy is often referred to as the “heat of reaction’— weights in Data Table 1 in your notebook. é 5. Take about 60 mL. of 95% v/v ethanol solution to your fume hood in a clean, dry100 mL. beaker. Draw out some ethanol with a Pasteur pipet and carefully dissolve the solid in your beaker in a minimum amount of ethanol. Transfer this solution into a 50-mL volumetric flask, rinsing the beaker 3-4 times with small amounts of ethanol. Fill the volumetric flask wit ehanol ro che mark. Mix comple, shen fill one cure wth your prepared opbalt solution, and another cuvette (the blank) with only ethanol. 6. Filla 250 mL beaker halfway with ice and add a heaping tablespoon of table salt. Stir thor- oughly with a clean stirring rod. Fill che rest of the beaker with ice, add another portion of salt, and stir again. Your salt bath should now be a thick slush, and there should be signifi cant frost on the sides of the beaker, If there is any appreciable amount of warer in your salt bath, carefully pour the water into the sink and add more ice and sal to fill the beaker. Place a thermometer (not the electronic thermometer!) in your salt bath and wait for the tempera- ture to stabilize; the final temperature should be no higher than -8°C.(Chemistry 122 Laboratory Mantal | Dr Annamaria Fulep 7. Place the cuvette containing your CoCl;'6H,0 in ethanol solution in the salt bath and leave it for at east 15 minutes. While the cuvette with the Co complex is cooling in the ice bath, place the cuvette with the blank solution into the spectrometer, Close the lid, and set the absorbance to zero. Remove the blank. . . « 8. When the time has elapsed, record the final temperature of yout ice bath into Data Table I. ‘Then quickly take the cuverte ont, wipe it dry, and place it in your spéctrometer. Move the ‘ ring stand so that the temperature probe rests in the solution exactly as it did in step 3. Place “+ the black light-blocking cup over the setup. Using black tape, tape the cup down onto the sur- face of the spectrometer, making sure to leave no space for light to enter, and prepare to record temperature and absorbance readings into the-second data table prepared in your notébook. ‘Wait until the temperature reading on the temperature probe stabilizes (there will be a period of fairly rapid beating up to pethaps -5 degrees C) then begin collecting absorbance data. Take an absorbance reading every 0.5 degrees C in temperature you read on the temperature probe; record both the temperature on the probe and the absorbance value. When the temperature of the solition increases to above 15°C, remove the setup and take the cuvette out. SSORRA Nh enenenee tenet ee eee eee eee ee HR - Data Table 1: 4. -mycight of beaker + solid CoCl,*6H,0 weight of empry beaker weight of solid CoCl,'6H,0 Table 2: ==; Co Calculations : 1. Before you begin your calculations, make an Excel spreadsheet in which to record your data and results. Create columns with the following headings for these values (in this or- der): Temperature (C), Absolute Temperature, Absorbancegssamy [Co(EOH) (C1), {Co(EtOH),(C),J, [EtOH], K,, and AG". Make sure to indicate the appropriate units of these values in your headings! For the calculations of these values you may use a formula in Exce, but be sure to write out the calculations for your first row of values in your lab report as well, labeling your calculations and final answers clea. From the weight of CoCly'6H,O, calculate the total molar concentration of cobalt ionsin your CoCly6H,0 in ethanol solition. Show all your calculations for your concentration of cobalt in your lab report and label your answer clearly. 3. Given that the molar absorptivity constant (e) for [Co(EtOH),(Cl),] is 66.871 M"! car, -use equation A=ebc to calculate the concentration of [Co(EtOH),(Cl),] at each of your recorded temperatures, Use the Beer-Lambert equation, A=ebc, where 6 is the path length of the light through the solution (the diameter of the cuvette), and is the concentration of the light-absorbing component at the given wavelength. Record these concentration values under “ the appropriate heading in your Excel spreadsheet. 4. Assuming thit all cobal ions this solution must be present as [Co(EOH)2(Ch,} or, [Co(EtOH)4(Cl)], youcan use the known total concentration of cdbalt ions calculated Q Step 2 and your equilibritum concentrations of [Co(EtOH),(Cl),] to culate the equilibti- tum concentrations of (Co(EtOH)4(C))9] at each of your recorded temperatures. Record these concentration values under the appropriate heading in your Excel spreadsheet. 5. ‘The molar concentration of the ethanol you used to make your solution is not given directly, however, you can calculate ic from the given mass % and density. (95% ethanol by mass, d = 0.789 g/ml. at room temperature). The given density value of ethanol does not deviate significantly over the temperature range employed in this experiment, Show all your calcula tions for your concentration of ethanol in your lab report and label your answer clearly. 6. Assuming that all echanol molecules in this solution must be present as free molecules or part of the two cobalt complexes, you can use your initial concentration of ethanol calculated in Step 5 and your calculated equilibrium concentrations of the two cobalt complexes from Steps 3 and 4 to find the equilibrium concentrations of ethanol at cach temperature, Record these concentration values under the appropriate heading in your Excel spreadsheet.(Chemistry 122 Laboratory Manual | Dr. Annamaria Fulep 7. Apply equation 2 for your reaction and calculate the value of the equilibrium constant at cach recorded temperature. Record the calculated K,, values under the appropriate heading in your Excel spreadsheet. 8. Use equation 3 to calculate AG? for this reaction at cach of your recorded temperatures. Re- cord these AG? values under the appropriate heading in your Excel spreadsheet. 9. Make a plot of your calculated values of AG* vs. the Kelvin temperature, titling your graph and labeling your axes appropriately (including units). Add a linear trend line to your data and display the equation. Which thermodynamic value does the slope of this trend line give tus? Which value does the intercept give us? Give clear identifying labels to these values in the trend line equation on your graph, specifying their unis as well Be sure to include your graph with your chart when handing in your lab report. ~ asegeeanennannnnanannnannnnen>. » ‘Thermodynamics of Cobalt Complexation | a — — nee » — Post-Lab Questions . » ' 1, Based on the data given by your graph, is this reaction endothermic or exothermic? Explai ” | ». . P ‘ » » . “ » » 2. Based on the data given by your graph, is this reaction accompanied by an increase or de- » crease of entropy? Looking at the reaction itself, support your answer with your knowledge of » entropy. , » 7 . ’ . ae oe 7 ~ e “ he 3. Using the equation given by the linear trend line of your AG® vs. temperature plot, calculate the value of AG? at standard conditions (298 K). ad ediedy * Hedin el aNeNNated dtd |» 2Mn?*(aq) + 10CO,(g) + 8H0() (Eq.3) Oxalate ions react rather slowly at room temperature so the solutions will be titrated at afound 85°C to accelerate the reaction for a convenient titration. Since the violet permanganate ion reduces to tHe colorless Mn’? ion, no additional indicator is needed for the titration. The KMnO, will continue turning colorless upon addition to the solution of C,O7 ions until there is no more C,O}" present. ‘The next fraction of a drop of KMnO, titrant will color the reaction mixture faint pink, indicating the endpoint of the titration, Pee PPE PE ee es‘Preparition and Standardization ofa KMn04 Solution Pre-Lab Questions : 1, Determine the oxidation number of the elements in each of the following compounds: ” a) H,CO, d) Ny b) Noy © LH " ©) Fe;Og 2. Balance each of the following reactions: a) As(s) + Cl, (g) + AsCl(s) 'b)_ Cu(s) + HNO;(aq) -» Cu?*(aq) + NO(g) (in acidic solution) , ©) MnO4(aq) + F-(aq) + Mn?*(aq) + 1,(6) (in acidic solution) > :(Chemistry 12a Laboratory Manual | Dr. Annamaria Fulep Procedure . Caution! KMnO, (potassium permanganate) stains skin and clothes, and the purple color changes to dark brown. It will wear off the skin with normal washing, but will cause 2 permanent stain on clothing. ’ Preparation of the KMnO, solution: 1. Ina small vial weigh out 4.5-5.0 g of KMnO,. Empty the contents into a clean 500-mL flask. Using a 100-ml. graduated cylinder, add about 100 mL of distilled water to the flask; swirl and mix well; add another 100-ml. of distilled water, mix and swirl; continue until a total of 400 ml. of distilled water has been added. 2, This solution is so dark that itis difficult to find out ifall of the potassium permanganate has dissolved, Heat the solution with occasional switling to dissolve the KMnO, crystals. Do not boil the solution! To check if al solid has dissolved, you can carefully pour the solution into another large container to see if some‘un-dissolved solid is left in the original flask. If so, pour it back and continue to stir and swirl. This may take up to 30 minutes, Obtain a 50-mL buret, clean it, rinse ita couple of times with distiled}water,then twice _ ‘with about 10-mL of Your KMnO, solution. Discard the rinsing’ in-the waste container in the hood: Fill che buret with the KMnO, solution, making sure that the tip caiains no ais, ‘ bubbles. Record the initial buret reading, Because the KMaO, solution is strongly colored the top of the meniscus may be read instead of the bottom. Titration of the KMn0O, solution: 1, Tare a small beaker (50 mL) on the top-loading balance. Add approximately 0.6 grams of pure sodium oxalate, NajC,0, (FW = 133.96) into the beaker. This amount will be enough for three titrations. Take the beaker with irs contents to the analytical balance and weigh it to the nearest 0.1 mg. Record the weight of beaker and NagCj04 measured in your data table. \ 2. Transfer about 1/3 of the NayC,O, into a 250-ml. Erlenmeyer fask. Add 50 mL. of distilled water and 20 mL of 3M HSO, to the oxalate sample in the Erlenmeyer flask. Heat the acidified solution to about 85 °C. Do not boil it! 3. Titrate the hot oxalate solution with the KMnO, in the buret until the appearance of a persistent faint pink color. Record the final buret reading. Discard the titration mixture down the drain. Refill your buret with the KMnO, solution. 280008 EEEE BEEBEPreparation and Standardization of a KMaO4 Solution “Transfer half of the remaining solid oxalate from the small beaker into a 250-mL Erlenmeyer flask. Record the weight of the small beaker with the last of the oxalate sample left inside. Add 50 mL of distilled water, 20 mL. of the 3M H,SO, and heat the solution like in step 4. ‘Titrate it like described in step 5. == . 5. Perform the last tiation with the oxalate left in the small beaker like described above. Make . sure you weigh and record the mass of the small beaker after removal of the third oxalate : sample, Afterall three titrations have been performed, an oxalic acid solution may be used to wash the buret and the titration flask ifa brown stain remains in the glassware. 6. Transfer your KMinO, solution into a clean, dry bottle using a clean, dry funnel, cap the bottle, and save it for next week. Data and Calculations Approximate mass of KMinO, in vial: ‘Mass of beaker + 3x ~0.2g Na,C,O4 4 ‘Mass of beaker + 2x ~ 0.2g Na,C,O4 wd + a Mass of beaker + 1x~0.2gNa,C,0, Mass of beaker after removing all NajC,O,, 1, Calculate the mass of each NayC,O, sample used by determining the decrease in mass of the small beaker after each removal of a sample. Record the masses in the table below for the mass of oxalate used for each titration. Also, record the final and initial volumes of the KMn0, solution for all three trials below. Mass of NagC,O4 used for tt Final buret reading (aL) Initial buret reading (mL) v(Chemistry 122 Laboratory Manual | Dr. Annamaria Fulep 2 7. i. Calcillation Results: - : » Molés of NagCjO4 titrated Convert the mass of NayC;O, in each titration to moles (FW=134.0), Record the values in the appropriate cells in the Calculation Results table below. Using the mole ratio between the KMnOg and Na,C,0, reacting, determine the moles of KMn0 reacting in each titration and record the values in the appropriate cells in the table. 2moles of KMnO, ‘Smolof NazC,0, Calculate the mL of KMnO, solution used for cach titration by finding the difference be- ‘tween the final and initial volume of KMnO, in the buret for the given trial. Convert those volumes to L and record the values in the Calculation Results table below. mokes of KMnO, = moles of NayC,0, - Divide the L of KMnO, solution used into the moles of KMnO, for each trial. Calculate an average molarity for the KMinO, solution by taking the average of the molari- ties found in the three trials. : Show all your detailed calculations in your lab report. BT Moles of KMnO, used Lof KMnQ, used ‘Molatity of KMnO, Average molariy of KMnOyPreparation and Standardization of a KMa0¥4 Solution Post-Lab Questions once 1. Given two possible formulas: K[Fe(C,0,4)2(H20),] or K3[Fe(C,0,)5}, a titration of 1.356 g of the compound (one of the two formulas above) requires 34.5 mL of 0.108M KMnO,.” Which formula matches the compound being titrated? 2. A1.2516 grams sample of a mixture of CaCO and Na,SOj was analyzed by dissolving the Sample.and.coinpletely precipitating the Ca?* as CaC,O,. ‘The Ca@,0j was dissolved in sulfurit.acid-and thé tesulting HyC)O, was titrated with a standard KMnOj solution. The titration required 35.62 milliliters of 0.1092 M KMnQ,. Calculate the number of moles of HC,, that reacted with the KMnO,. Calculate the number of moles of CaCO; in the original sample. Calculate the percentage by weight of CaCO, in the original sample. asDetermining the Mass of Fe(II) in a Commercial Tron Supplement Pill by Redox Titration | (Week Two) = 4 Objectives To find the mass of Fe(II) in a commercial iron supplement by titrating a solution of a single dis- solved pill with a standard potassium permanganate solution. ‘The volume of the standard titrant determines the moles of KMnO, used for one tablet. The mole ratio from the redox reaction in- volved allows for the determination of the moles, and thus, the mass of the Fe(II) titrated. Introduction Iron supplements contain soluble iron({1) salts to replenish Fe(II) in the human body. Iron plays a critical role in the human circulatory system. The uptake of oxygen and the removal of carbon dioxide in the blood are carried out by the Fe atom in the center of the hemoglobin molecule. It is well known thata deficiency in iron can lead to a loss of hemoglobin and the onset of certain types of anemia. Those cases may require iron supplementation. Iron deficiency can occur through poor diet, or a a consequence of blood loss.122 Laboratory Manual | Dr. Annamaria Fulep Potassiurh permanganate reacts with Fe(II) salts according to the following oxidation-reduction reaction: 5x (Fe2* -» Fe3* +e") ‘oxidation MnOj + 8H* + Se" > Mn? + 4H,0. reduction ‘MnO; + 5Fe* + 8H" — SFe* + Mn +4H,0 overall reaction In this experiment you will titrate the solution made by dissolving an Fe(II) supplement tablet in an acidic environment and then titrating the Fe(II) in.the resulting sample with the standard KMnO, solution you prepared last week. Knowing the volume of the KMnO, solution needed to titrate the Fe({U) in the tablet as wel as the stoichiometry of the reaction, you will be able ro determine the moles and the mass (in mg) of Fe(II) that was present in the supplement pill. Your calculations will follow the scheme below: mL of KMnO, used -> mol of KMnO, -> mol of Fe** > g of Fe?* > mg of Fe* t t t t Molarity of SmolFe* MMofFe 1000 mg KMn0, 1 mol KMnO, Tg For each step of the calculations the conversions to be used is indicated. ‘Determining the Mass of F(t!) in a Commercial ron Supplement ill by Redox Titration Pre-Lab Questions b 1. IF 45.52 mL ofa potassium permanganate solution is needed to titrate 2.145 g of ferrous am- monium sulfate hexahydrate, (NH,),Fe(SO,),-6H,O, calculate the molarity of the KMnO, solution. . 2. 1.545 g solid sample of an unknown containing iron(II) in the dissolved sample requires 32.85 mL. of a 0.025 M KMnO, solution to reach the pink end point of the titration, Calcu- late the mass of iron in the sample (in grams) and the percentage of iron in the sample. ' 3. 0.2640 g of sodium oxalate is dissolved in a ask and requires 30.74 ml. of potassium per- 7 ‘manganate to titrate it to turn pink end point. ‘The equation for this reaction is: , » » ” ’ , » » » » » » » » » 5NazC,0, + 2KMnO, + 8H,SO, > 2Mn$Oj #250, + SNa,S0, + 10CO; + 8H,0 , a) How many moles of sodium oxalate are present in thé flask? b) How many moles of potassium permanganate have been titrated into the lask to reach the end point? ) Whats the molarity of the potassium permanganate? core ygrrrrrcrssscsss(Chemistry 122 Laboratory Manual | Dr. Annamaria Fulep Procedure 1. Obtain a clean 250-mL volumetric flask. Transfer exactly 50.00 mL. of the standard KMnOy solution you prepared the week before into the volumetric flask using volumetric pipettés and dilute ie with distilled water to the mark. Stopper the flask with a fiting glass stopper. Homogenize the solution thoroughly by turning the flask upside down a few times, securing the stopper in place in place with your thumb. 2. Assemble a titration set-up. Rinse the buret first with distilled warer, then with the diluted permanganate solution from the volumetric flask several times. Fill the buret with permanga- nate solution you prepared last week and record the initial volume of the KMnO, solution in your data table. 3. Obtain a mortar and pestle. Place one pill into the mortar and crush it into a powder. Trans- fer the crushed pill quantitatively to a 250-mL Erlenmeyer flask, rinsing with small por- tions of distilled water for complete transfer, Add 50 ml of 1.0 M H,SO, solution to the iron sample and increase the solution volume with distilled water to a final volume of about 100 mL. of solution in the Erlenmeyer flask. Dissolve the sample as completely as possible. (Some heating may be needed.) The resulting solution will not be completely clear; some of the fill- ers used in the manufacturing of the pill will spake it look cloudy. This will not interfere with dbraining accurate results. + . ; S 4. Immediately titrate the iron solution with the standard KMnO, solution. As the permanga- nate solution is added to the sample, a light yellow color may develop in the iron solution that could interfere with an easy endpoint detection. This can be remedied by the addition of phosphoric acid. The appearance of the yellow color is due to the presence of chloride ions in the solution, which form a yellow complex with the Fe** ions. The addition of 3 mL of 85% HPO, to the solution converts the chloro complex of Fe(III) to the phosphate com- plex which is colorless, thus, does not interfere with the endpoint detection. Swirl the flask constantly until the first appearance of a pale pink color that persists for 30 seconds. Record the final volume in your data table. 5. Repeat the titration two more times with new samples of the Fe supplement prepared as described in Step 3. 6. Perform a two more titrations now using the standard KMnO, solution pravided in the laboratory. Make sure your own KMnQ, solution is now drained and rinsed out of the buret, and you rinse the buret with the KMnO, solution provided in the lab. BARRA ARAAMRARARAAAAMAAABRABAABAAAAABDABAASD ROADDetermining the Mass ofFe(1}) in a Commercial Ion Supplement Pill by Redox Titration . Data . cen one Teial 3 coe a DON et at aco KMnQ, froin lab Initial volume of KMnO, 7 Final volume of KMnO, Calculations ' KMnO, prepared previous week KMnQ, from lab ; Volume of KMnOg used ' Moles of KMnO, used : Moles of Fein pill 7 » 7 eo Grams of Fe in pill °2] ‘Migs of Fe in pill pe” fot af oy 7 v—(Chemistry 123 Laboratory Mancal | Dr. Annamaria Fulep Post-Lab Questions ' | 1. Compare your results berween the KMnO, solution you ptepared and the solution provided | by the lab. Are they similar? If not, what do you think the reason is for the difference? wl 2. What isthe purpose of dissolving the iron supplement pillin HySO, and why is phosphoric acid added later on during the titration? 3. Balance’ the following redox equation: * r an ie 7 Fe*(aq) + Cr,0;7 (aq) + Ht -> Fe3*(aq) + Cr3*(aq) + HO. a“ “ 4, Asolution of iron(II) sulfate was prepared by dissolving 10.00 g of FeSO,*7H,O (FW = 277.9) in water and diluting up to a total volume of 250 mL. The solution was left to stand, exposed to ait, and some of the iron(II) ions became oxidized to ron(HIl) ions. A 25.0 mL. sample of this partially oxidized solution required 23.70 mL of 0.0100 M potassium dichro* Aa mate KCr,O7 solution for complete reaction in the presence of dilute sulfuric acid. Cal- culate the percentage of iron(II) ions that had been oxidized by the air. You need to use the balanced redox reaction in question 3. in order to complete your calculations. 1 ' ay (i ‘ ( ( ( ( ( ( i 24 f 4 4 4 “4 4 ‘ 4 ‘ 4 ‘ cy q a c a « « a a