zhVGV9 hH CJ OJ QJ ^J aJ h 5CJ OJ QJ ^J aJ #h hH 5CJ OJ QJ ^J aJ #hk h(5 5CJ OJ QJ ^J aJ h(5 CJ OJ QJ ^J aJ $h(5 h(5 5B* 0000016796 00000 n Method C, the EDTA titration method, measures the calcium and magnesium ions and may be applied with appro-priate modication to any kind of water. Titration 2: moles Ni + moles Fe = moles EDTA, Titration 3: moles Ni + moles Fe + moles Cr + moles Cu = moles EDTA, We can use the first titration to determine the moles of Ni in our 50.00-mL portion of the dissolved alloy. Show your calculations for any one set of reading. CJ H*OJ QJ ^J aJ h`. We will also need indicator - either in the form of solution, or ground with NaCl - 100mg of indicator plus 20g of analytical grade NaCl. Figure 9.29b shows the pCd after adding 5.00 mL and 10.0 mL of EDTA. Obtain a small volume of your unknown and make a 10x dilution of the unknown. Calculate the Aluminum hydroxide and Magnesium hydroxide content in grams in the total diluted sample. When the titration is complete, raising the pH to 9 allows for the titration of Ca2+. where Kf is a pH-dependent conditional formation constant. When the reaction between the analyte and titrant is complete, you can observe a change in the color of the solution or pH changes. EDTA (mol / L) 1 mol Calcium. Step 3: Calculate pM values before the equivalence point by determining the concentration of unreacted metal ions. Figure 9.33 Titration curves for 50 mL of 103 M Mg2+ with 103 M EDTA at pHs 9, 10, and 11 using calmagite as an indicator. Calcium is determined at pH 12 where magnesium is quantitatively precipitated as the hydroxide and will not react with EDTA. Preparation of 0.025M MgSO4.7H2O: Dissolve 0.616 grams of analytic grade magnesium sulfate into a 100 mL volumetric flask. Your TA will give you further information on how you will obtain your data. Figure 9.29 Illustrations showing the steps in sketching an approximate titration curve for the titration of 50.0 mL of 5.00 103 M Cd2+ with 0.0100 M EDTA in the presence of 0.0100 M NH3: (a) locating the equivalence point volume; (b) plotting two points before the equivalence point; (c) plotting two points after the equivalence point; (d) preliminary approximation of titration curve using straight-lines; (e) final approximation of titration curve using a smooth curve; (f) comparison of approximate titration curve (solid black line) and exact titration curve (dashed red line). Determination of Hardness: Hardness is expressed as mg/L CaCO 3. When the reaction is complete all the magnesium ions would have been complexed with EDTA and the free indicator would impart a blue color to the solution. \[\alpha_{\textrm Y^{4-}} \dfrac{[\textrm Y^{4-}]}{C_\textrm{EDTA}}\tag{9.11}\]. @ A udRAdR3%hp CJ OJ QJ ^J aJ hLS CJ OJ QJ ^J aJ h, h% CJ OJ QJ ^J aJ #hlx% h% CJ H*OJ QJ ^J aJ h, h% CJ OJ QJ ^J aJ &hk hLS 5CJ OJ QJ \^J aJ h% 5CJ OJ QJ \^J aJ h 5CJ OJ QJ \^J aJ &h, h% 5CJ OJ QJ \^J aJ (hk h% CJ OJ QJ ^J aJ mHsH (hlx% h% CJ OJ QJ ^J aJ mHsH +hlx% hlx% 5CJ OJ QJ ^J aJ mHsH A D ` h k o r { y z " # 3 4 I J V { yk hlx% CJ OJ QJ ^J aJ ,h(5 h% 5B* EDTA (L) Molarity. The concentration of Cl in the sample is, \[\dfrac{0.0226\textrm{ g Cl}^-}{0.1000\textrm{ L}}\times\dfrac{\textrm{1000 mg}}{\textrm g}=226\textrm{ mg/L}\]. xref 3 22. Lets calculate the titration curve for 50.0 mL of 5.00 103 M Cd2+ using a titrant of 0.0100 M EDTA. The mean corrected titration volume was 12.25 mL (0.01225 L). It is widely used in the pharmaceutical industry to determine the metal concentration in drugs. Table 9.14 provides examples of metallochromic indicators and the metal ions and pH conditions for which they are useful. For the purposes of this lab an isocratic gradient is used. 2. To do so we need to know the shape of a complexometric EDTA titration curve. A complexometric titration method is proposed to determine magnesium oxide in flyash blended cement. Beginning with the conditional formation constant, \[K_\textrm f'=\dfrac{[\mathrm{CdY^{2-}}]}{[\mathrm{Cd^{2+}}]C_\textrm{EDTA}}=\alpha_\mathrm{Y^{4-}} \times K_\textrm f = (0.37)(2.9\times10^{16})=1.1\times10^{16}\], we take the log of each side and rearrange, arriving at, \[\log K_\textrm f'=-\log[\mathrm{Cd^{2+}}]+\log\dfrac{[\mathrm{CdY^{2-}}]}{C_\textrm{EDTA}}\], \[\textrm{pCd}=\log K_\textrm f'+\log\dfrac{C_\textrm{EDTA}}{[\mathrm{CdY^{2-}}]}\]. 5CJ OJ QJ ^J aJ h`. Next, we draw our axes, placing pCd on the y-axis and the titrants volume on the x-axis. Thus one simply needs to determine the area under the curve of the unknown and use the calibration curve to find the unknown concentration. ! The titration is done with 0.1 mol/l AgNO3 solution to an equivalence point. Although each method is unique, the following description of the determination of the hardness of water provides an instructive example of a typical procedure. Furthermore, lets assume that the titrand is buffered to a pH of 10 with a buffer that is 0.0100 M in NH3. Calculate the total millimoles of aluminum and magnesium ions in the antacid sample solution and in the tablet. h% 5>*CJ OJ QJ ^J aJ mHsH +h, h, 5CJ OJ QJ ^J aJ mHsH { ~ " : kWI8 h, h% CJ OJ QJ ^J aJ hp CJ OJ QJ ^J aJ &h, h% 5CJ OJ QJ \^J aJ &hk hLS 5CJ OJ QJ \^J aJ &hLS h% 5CJ OJ QJ \^J aJ hlx% 5CJ OJ QJ \^J aJ hs CJ OJ QJ ^J aJ &h, h, 6CJ OJ QJ ]^J aJ )hs h% 6CJ H*OJ QJ ]^J aJ hs 6CJ OJ QJ ]^J aJ &h, h% 6CJ OJ QJ ]^J aJ : $ ( * , . %Srr~81@ n0/Mm`:5 A)r=AKVvY Ri9~Uvhug BAp$eK,v$R!36e8"@` This can be done by raising the pH to 12, which precipitates the magnesium as its hydroxide: Mg2+ + 2OH- Mg(OH) 2 \[K_\textrm f''=\dfrac{[\mathrm{CdY^{2-}}]}{C_\textrm{Cd}C_\textrm{EDTA}}=\dfrac{3.33\times10^{-3}-x}{(x)(x)}= 9.5\times10^{14}\], \[x=C_\textrm{Cd}=1.9\times10^{-9}\textrm{ M}\]. and pCd is 9.77 at the equivalence point. What problems might you expect at a higher pH or a lower pH? The most likely problem is spotting the end point, which is not always sharp. The buffer is at its lower limit of pCd = logKf 1 when, \[\dfrac{C_\textrm{EDTA}}{[\mathrm{CdY^{2-}}]}=\dfrac{\textrm{moles EDTA added} - \textrm{initial moles }\mathrm{Cd^{2+}}}{\textrm{initial moles }\mathrm{Cd^{2+}}}=\dfrac{1}{10}\], Making appropriate substitutions and solving, we find that, \[\dfrac{M_\textrm{EDTA}V_\textrm{EDTA}-M_\textrm{Cd}V_\textrm{Cd}}{M_\textrm{Cd}V_\textrm{Cd}}=\dfrac{1}{10}\], \[M_\textrm{EDTA}V_\textrm{EDTA}-M_\textrm{Cd}V_\textrm{Cd}=0.1 \times M_\textrm{Cd}V_\textrm{Cd}\], \[V_\textrm{EDTA}=\dfrac{1.1 \times M_\textrm{Cd}V_\textrm{Cd}}{M_\textrm{EDTA}}=1.1\times V_\textrm{eq}\]. 0000008621 00000 n The scale of operations, accuracy, precision, sensitivity, time, and cost of a complexation titration are similar to those described earlier for acidbase titrations. 5. Once again, to find the concentration of uncomplexed Cd2+ we must account for the presence of NH3; thus, \[[\mathrm{Cd^{2+}}]=\alpha_\mathrm{Cd^{2+}}\times C_\textrm{Cd}=(0.0881)(1.9\times10^{-9}\textrm{ M}) = 1.70\times10^{-10}\textrm{ M}\]. State the value to 5 places after the decimal point. Even if a suitable indicator does not exist, it is often possible to complete an EDTA titration by introducing a small amount of a secondary metalEDTA complex, if the secondary metal ion forms a stronger complex with the indicator and a weaker complex with EDTA than the analyte. The second titration uses, \[\mathrm{\dfrac{0.05831\;mol\;EDTA}{L}\times0.03543\;L\;EDTA=2.066\times10^{-3}\;mol\;EDTA}\]. The total concentrations of Cd2+, CCd, and the total concentration of EDTA, CEDTA, are equal. You can review the results of that calculation in Table 9.13 and Figure 9.28. Although EDTA forms strong complexes with most metal ion, by carefully controlling the titrands pH we can analyze samples containing two or more analytes. Standard magnesium solution, 0.05 M. Dissolve 1.216 g of high purity mag- nesium (Belmont 99.8%) in 200 ml of 20% hydrochloric acid and dilute to 11. 243 26 Finally, complex titrations involving multiple analytes or back titrations are possible. xb```a``"y@ ( Reporting Results " " " # # ?$ zS U gd% gd% m$ gd m$ d 7$ 8$ H$ gdp d 7$ 8$ H$ gd% n o ( ) f lVlVlVlVl +hlx% h% 5CJ OJ QJ ^J aJ mHsH+hlx% h% 5CJ OJ QJ ^J aJ mHsH(h- hlx% CJ OJ QJ ^J aJ mHsH hlx% CJ OJ QJ ^J aJ hp CJ OJ QJ ^J aJ hLS CJ OJ QJ ^J aJ hH CJ OJ QJ ^J aJ h, h% CJ OJ QJ ^J aJ #h0 h0 CJ H*OJ QJ ^J aJ h0 CJ OJ QJ ^J aJ 4 6 7 = ? seems!to!proceed!slowly!near!the!equivalence!point,!after!each!addition!of! The concentration of Cd2+, therefore, is determined by the dissociation of the CdY2 complex. The sample is acidified to a pH of 2.33.8 and diphenylcarbazone, which forms a colored complex with excess Hg2+, serves as the indicator. We can account for the effect of an auxiliary complexing agent, such as NH3, in the same way we accounted for the effect of pH. Step 2: Calculate the volume of EDTA needed to reach the equivalence point. To calculate magnesium solution concentration use EBAS - stoichiometry calculator. The specific form of EDTA in reaction 9.9 is the predominate species only at pH levels greater than 10.17. Unfortunately, because the indicator is a weak acid, the color of the uncomplexed indicator also changes with pH. Magnesium ions form a less stable EDTA complex compared to calcium ions but a more stable indicator complex hence a small amount of Mg2+ or Mg-EDTA complex is added to the reaction mixture during the titration of Ca2+ with EDTA. In general this is a simple titration, with no other problems then those listed as general sources of titration errors. Dilute 20ml of the sample in Erlenmeyer flask to 40ml by adding 20ml of distilled water. Reactions taking place The solution is warmed to 40 degrees C and titrated against EDTA taken in the burette. The experimental approach is essentially identical to that described earlier for an acidbase titration, to which you may refer. About Press Copyright Contact us Creators Advertise Developers Terms Privacy Policy & Safety How YouTube works Test new features NFL Sunday Ticket Press Copyright . Calculation of EDTA titration results is always easy, as EDTA reacts with all metal ions in 1:1 ratio: That means number of moles of magnesium is exactly that of number of moles of EDTA used. MgSO4 Mg2++SO42- Experimental: [\mathrm{CdY^{2-}}]&=\dfrac{\textrm{initial moles Cd}^{2+}}{\textrm{total volume}}=\dfrac{M_\textrm{Cd}V_\textrm{Cd}}{V_\textrm{Cd}+V_\textrm{EDTA}}\\ The method adopted for the Ca-mg analysis is the complexometric titration. The earliest examples of metalligand complexation titrations are Liebigs determinations, in the 1850s, of cyanide and chloride using, respectively, Ag+ and Hg2+ as the titrant. Note that after the equivalence point, the titrands solution is a metalligand complexation buffer, with pCd determined by CEDTA and [CdY2]. PAGE \* MERGEFORMAT 1 U U U U U U U U U. ! Calculate the number of grams of pure calcium carbonate required to prepare a 100.0 mL standard calcium solution that would require ~35 mL of 0.01 M EDTA for titration of a 10.00 mL aliquot: g CaCO 3 = M EDTA x 0.035L x 1 mol CaCO 3/1 mol EDTA x MM CaCO 3 x 100.0mL/10.00mL 3. Calcium and Magnesium ion concentration determination with EDTA titration 56,512 views Dec 12, 2016 451 Dislike Share Save Missy G. 150 subscribers CHEM 249 Extra credit by Heydi Dutan and. Determination of Permanent hardness Take 100 ml of sample hard water in 250 ml beaker. See the text for additional details. Solving gives [Cd2+] = 4.71016 M and a pCd of 15.33. The Titration After the magnesium ions have been precipitated out of the hard water by the addition of NaOH (aq) to form white Mg(OH) 2(s), the remaining Ca 2+ ions in solution are titrated with EDTA solution.. In the initial stages of the titration magnesium ions are displaced from the EDTA complex by calcium ions and are . The quantitative relationship between the titrand and the titrant is determined by the stoichiometry of the titration reaction. in triplicates using the method of EDTA titration. Both magnesium and calcium can be easily determined by EDTA titration in the pH 10 against Eriochrome Black T. If the sample solution initially contains also other metal ions, one should first remove or mask them, as EDTA react easily with most of the cations (with the exception of alkali metals). Because we use the same conditional formation constant, Kf, for all calculations, this is the approach shown here. In this study Other metalligand complexes, such as CdI42, are not analytically useful because they form a series of metalligand complexes (CdI+, CdI2(aq), CdI3 and CdI42) that produce a sequence of poorly defined end points. Figure 9.27 shows a ladder diagram for EDTA. 0000002034 00000 n Figure 9.29a shows the result of the first step in our sketch. The operational definition of water hardness is the total concentration of cations in a sample capable of forming insoluble complexes with soap. is large, its equilibrium position lies far to the right. See Chapter 11 for more details about ion selective electrodes. Figure 9.28 Titration curve for the titration of 50.0 mL of 5.00103 M Cd2+ with 0.0100 M EDTA at a pH of 10 and in the presence of 0.0100 M NH3. C_\textrm{Cd}&=\dfrac{\textrm{initial moles Cd}^{2+} - \textrm{moles EDTA added}}{\textrm{total volume}}=\dfrac{M_\textrm{Cd}V_\textrm{Cd}-M_\textrm{EDTA}V_\textrm{EDTA}}{V_\textrm{Cd}+V_\textrm{EDTA}}\\ The analogous result for a complexation titration shows the change in pM, where M is the metal ion, as a function of the volume of EDTA. Step 5: Calculate pM after the equivalence point using the conditional formation constant. We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. 2. A similar calculation should convince you that pCd = logKf when the volume of EDTA is 2Veq. 0000021941 00000 n Why does the procedure specify that the titration take no longer than 5 minutes? All Answers (10) 1) Be sure the pH is less than 10, preferably about 9.5-9.7. The sample, therefore, contains 4.58104 mol of Cr. Estimation of magnesium ions in the given sample: 20 mL of the given sample of solution containing magnesium ions is pipetted into a 250 Erlenmeyer flask, the solution is diluted to 100 mL, warmed to 40 degrees C, 2 mL of a buffer solution of pH 10 is added followed by 4 drops of Eriochrome black T solution. The solution was then made alkaline by ammonium hydroxide. Adding a small amount of Mg2+EDTA to the buffer ensures that the titrand includes at least some Mg2+. Report the molar concentration of EDTA in the titrant. The first four values are for the carboxylic acid protons and the last two values are for the ammonium protons. As is the case with acidbase titrations, we estimate the equivalence point of a complexation titration using an experimental end point. 0000023793 00000 n 0000002921 00000 n (Use the symbol Na 2 H 2 Y for Na 2 EDTA.) Figure 9.33 shows the titration curve for a 50-mL solution of 103 M Mg2+ with 102 M EDTA at pHs of 9, 10, and 11. The next task in calculating the titration curve is to determine the volume of EDTA needed to reach the equivalence point. ^208u4-&2`jU" JF`"Py~}L5@X2.cXb43{b,cbk X$ Background Calcium is an important element for our body. The titration is performed by adding a standard solution of EDTA to the sample containing the Ca. Figure 9.29c shows the third step in our sketch. A spectrophotometric titration is a particularly useful approach for analyzing a mixture of analytes. Transfer a 10.00-mL aliquot of sample to a titration flask, adjust the pH with 1-M NaOH until the pH is about 10 (pH paper or meter) and add .