Compare your results with Figure 9.28 and comment on the effect of pH and of NH3 on the titration of Cd2+ with EDTA. To illustrate the formation of a metalEDTA complex, lets consider the reaction between Cd2+ and EDTA, \[\mathrm{Cd^{2+}}(aq)+\mathrm{Y^{4-}}(aq)\rightleftharpoons \mathrm{CdY^{2-}}(aq)\tag{9.9}\], where Y4 is a shorthand notation for the fully deprotonated form of EDTA shown in Figure 9.26a. Complexometric titration is used for the estimation of the amount of total hardness in water. An alloy of chromel containing Ni, Fe, and Cr was analyzed by a complexation titration using EDTA as the titrant. Solutions of EDTA are prepared from its soluble disodium salt, Na2H2Y2H2O and standardized by titrating against a solution made from the primary standard CaCO3. In the method described here, the titrant is a mixture of EDTA and two indicators. Complexometric Determination of Magnesium using EDTA EDTA Procedure Ethylenediaminetetraacetic Acid Procedure Preparing a Standard EDTA Solution Reactions 1.Weighing by difference 0.9g of EDTA 2.Quantitatively transfer it to a 250 mL volumetric flask 3.Add a 2-3mL of amonia buffer (pH 10) 0.2 x X3 xY / 1 x 0.1 = Z mg of calcium. A late end point and a positive determinate error are possible if we use a pH of 11. ! 0000001920 00000 n of standard calcium solution are assumed equivalent to 7.43 ml. where VEDTA and VCu are, respectively, the volumes of EDTA and Cu. The best way to appreciate the theoretical and practical details discussed in this section is to carefully examine a typical complexation titrimetric method. EDTA (L) Molarity. A time limitation suggests that there is a kinetically controlled interference, possibly arising from a competing chemical reaction. The operational definition of water hardness is the total concentration of cations in a sample capable of forming insoluble complexes with soap. Because the color of calmagites metalindicator complex is red, its use as a metallochromic indicator has a practical pH range of approximately 8.511 where the uncomplexed indicator, HIn2, has a blue color. The displacement by EDTA of Mg2+ from the Mg2+indicator complex signals the titrations end point. Before the equivalence point, Cd2+ is present in excess and pCd is determined by the concentration of unreacted Cd2+. A second 50.00-mL aliquot was treated with hexamethylenetetramine to mask the Cr. 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. After transferring a 50.00-mL portion of this solution to a 250-mL Erlenmeyer flask, the pH was adjusted by adding 5 mL of a pH 10 NH3NH4Cl buffer containing a small amount of Mg2+EDTA. Complexation titrations, however, are more selective. The reaction that takes place is the following: (1) C a 2 + + Y 4 C a Y 2 Before the equivalence point, the Ca 2+ concentration is nearly equal to the amount of unchelated (unreacted) calcium since the dissociation of the chelate is slight. Add 4 drops of Eriochrome Black T to the solution. An analysis done on a series of samples with known concentrations is utilized to build a calibration curve. Chloride is determined by titrating with Hg(NO3)2, forming HgCl2(aq). Step 4: Calculate pM at the equivalence point using the conditional formation constant. The indicator changes color when pMg is between logKf 1 and logKf + 1. 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 : $ ( * , . Neither titration includes an auxiliary complexing agent. hbbe`b``3i~0 If MInn and Inm have different colors, then the change in color signals the end point. Most metallochromic indicators also are weak acids. Magnesium levels in drinking water in the US. One way to calculate the result is shown: Mass of. 21 0 obj <> endobj Figure 9.27 shows a ladder diagram for EDTA. 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. From the chromatogram it is possible to get the area under the curve which is directly related to the concentration of the analyte. A titration of Ca2+ at a pH of 9 gives a distinct break in the titration curve because the conditional formation constant for CaY2 of 2.6 109 is large enough to ensure that the reaction of Ca2+ and EDTA goes to completion. 0000009473 00000 n Let the burette reading of EDTA be V 2 ml. The intensely colored Cu(NH3)42+ complex obscures the indicators color, making an accurate determination of the end point difficult. 0000020364 00000 n Correcting the absorbance for the titrands dilution ensures that the spectrophotometric titration curve consists of linear segments that we can extrapolate to find the end point. In 1945, Schwarzenbach introduced aminocarboxylic acids as multidentate ligands. EDTA and the metal ion in a 1:1 mole ratio. In addition magnesium forms a complex with the dye Eriochrome Black T. 0 endstream endobj 244 0 obj <>/Metadata 80 0 R/Pages 79 0 R/StructTreeRoot 82 0 R/Type/Catalog/ViewerPreferences<>>> endobj 245 0 obj <>/ExtGState<>/Font<>/ProcSet[/PDF/Text]>>/Rotate 0/StructParents 0/TrimBox[0.0 0.0 595.276 841.89]/Type/Page>> endobj 246 0 obj <> endobj 247 0 obj <>stream The reaction between Mg2+ ions and EDTA can be represented like this. 0000000881 00000 n Because the reactions formation constant, \[K_\textrm f=\dfrac{[\textrm{CdY}^{2-}]}{[\textrm{Cd}^{2+}][\textrm{Y}^{4-}]}=2.9\times10^{16}\tag{9.10}\]. A similar calculation should convince you that pCd = logKf when the volume of EDTA is 2Veq. Click n=CV button above EDTA4+ in the input frame, enter volume and concentration of the titrant used. Complexation Titration is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts. Submit for analysis. For the titration of Mg2+, one must buffer the solution to a pH of 10 so that complex formation will be quantitative. 0000001334 00000 n What problems might you expect at a higher pH or a lower pH? 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. Table 9.12 provides values of M2+ for several metal ion when NH3 is the complexing agent. and pCd is 9.77 at the equivalence point. Protocol B: Determination of Aluminum Content Alone Pipet a 10.00 ml aliquot of the antacid sample solution into a 125 ml. The solution is warmed to 40 degrees C and titrated against EDTA taken in the burette. Architektw 1405-270 MarkiPoland, free trial version of the stoichiometry calculator. A blank solution (distilled water) was also titrated to be sure that calculations were correct. 243 26 In addition to its properties as a ligand, EDTA is also a weak acid. We can solve for the equilibrium concentration of CCd using Kf and then calculate [Cd2+] using Cd2+. \[C_\textrm{EDTA}=[\mathrm{H_6Y^{2+}}]+[\mathrm{H_5Y^+}]+[\mathrm{H_4Y}]+[\mathrm{H_3Y^-}]+[\mathrm{H_2Y^{2-}}]+[\mathrm{HY^{3-}}]+[\mathrm{Y^{4-}}]\]. This leaves 8.50104 mol of EDTA to react with Cu and Cr. EDTA Titration Calculations The hardness of water is due in part to the presence of Ca2+ ions in water. &=\dfrac{(5.00\times10^{-3}\textrm{ M})(\textrm{50.0 mL})}{\textrm{50.0 mL + 25.0 mL}}=3.33\times10^{-3}\textrm{ M} &=\dfrac{(5.00\times10^{-3}\textrm{ M})(\textrm{50.0 mL}) - (\textrm{0.0100 M})(\textrm{5.0 mL})}{\textrm{50.0 mL + 5.0 mL}}=3.64\times10^{-3}\textrm{ M} The correction factor is: f = [ (7.43 1.5)/51/2.29 = 0.9734 The milliliters of EDTA employed for the calcium and the calcium plus mag- nesium titration are nmltiplied by f to correct for precipitate volume. EDTAwait!a!few!seconds!before!adding!the!next!drop.!! In this section we demonstrate a simple method for sketching a complexation titration curve. This reaction can be used to determine the amount of these minerals in a sample by a complexometric titration. The obtained average molarity of EDTA (0.010070.00010 M) is used in Table 2 to determine the hardness of water. The LibreTexts libraries arePowered by NICE CXone Expertand are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. 3: Hardness (in mg/L as CaCO 3 . The third titration uses, \[\mathrm{\dfrac{0.05831\;mol\;EDTA}{L}\times0.05000\;L\;EDTA=2.916\times10^{-3}\;mol\;EDTA}\], of which 1.524103 mol are used to titrate Ni and 5.42104 mol are used to titrate Fe. dh 7$ 8$ H$ ^gd Calculate the Aluminum hydroxide and Magnesium hydroxide content in grams in the total diluted sample. CJ OJ QJ ^J aJ h`. The indicators end point with Mg2+ is distinct, but its change in color when titrating Ca2+ does not provide a good end point. Solving gives [Cd2+] = 4.71016 M and a pCd of 15.33. Thus, by measuring only magnesium concentration in the All Answers (10) 1) Be sure the pH is less than 10, preferably about 9.5-9.7. 0000001283 00000 n 0000005100 00000 n Determination of Calcium and Magnesium in Water . Add 20 mL of 0.05 mol L1 EDTA solution. Figure 9.29a shows the result of the first step in our sketch. At the equivalence point we know that moles EDTA = moles Cd2 + MEDTA VEDTA = MCd VCd Substituting in known values, we find that it requires Veq = VEDTA = MCdVCd MEDTA = (5.00 10 3 M)(50.0 mL) 0.0100 M = 25.0 mL h, 5>*CJ OJ QJ ^J aJ mHsH .h To evaluate the relationship between a titrations equivalence point and its end point, we need to construct only a reasonable approximation of the exact titration curve. After the equivalence point, EDTA is in excess and the concentration of Cd2+ is determined by the dissociation of the CdY2 complex. Next, we solve for the concentration of Cd2+ in equilibrium with CdY2. Using the volumes of solutions used, their determined molarity, you will be able to calculate the amount of magnesium in the given sample of water. Although each method is unique, the following description of the determination of the hardness of water provides an instructive example of a typical procedure. hs 5>*CJ OJ QJ ^J aJ mHsH 1h For example, we can identify the end point for a titration of Cu2+ with EDTA, in the presence of NH3 by monitoring the titrands absorbance at a wavelength of 745 nm, where the Cu(NH3)42+ complex absorbs strongly. Titration is a method to determine the unknown concentration of a specific substance (analyte) dissolved in a sample of known concentration. For each of the three titrations, therefore, we can easily equate the moles of EDTA to the moles of metal ions that are titrated. Record the volume used (as V.). Determination of Hardness of Water and Wastewater. calcium and magnesium by complexometric titration with EDTA in the presence of metallo-chromic indicators Calcon or Murexide for Ca 2+ and Eriochrome Black T for total hardness (Ca 2+ + Mg 2+), where Mg 2+ is obtained by difference (Raij, 1966; Embrapa, 1997; Cantarella et al., 2001; Embrapa, 2005). Another common method is the determination by . The resulting metalligand complex, in which EDTA forms a cage-like structure around the metal ion (Figure 9.26b), is very stable. [\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}}\\ 0000000676 00000 n Determination of Hardness: Hardness is expressed as mg/L CaCO 3. A 0.1557-g sample is dissolved in water, any sulfate present is precipitated as BaSO4 by adding Ba(NO3)2. 0000023793 00000 n Although EDTA forms strong complexes with most metal ion, by carefully controlling the titrands pH we can analyze samples containing two or more analytes. Buffer . See Figure 9.11 for an example. For removal of calcium, three precipitation procedures were compared. Figure 9.30 (a) Predominance diagram for the metallochromic indicator calmagite showing the most important form and color of calmagite as a function of pH and pMg, where H2In, HIn2, and In3 are uncomplexed forms of calmagite, and MgIn is its complex with Mg2+. Finally, we can use the third titration to determine the amount of Cr in the alloy. Use the standard EDTA solution to titrate the hard water. It is used to analyse urine samples. Take a sample volume of 20ml (V ml). 5CJ OJ QJ ^J aJ h`. The equivalence point of a complexation titration occurs when we react stoichiometrically equivalent amounts of titrand and titrant. The pH affects a complexometric EDTA titration in several ways and must be carefully controlled. The concentration of Cd2+, therefore, is determined by the dissociation of the CdY2 complex. 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* Calculation. h`. In the process of titration, both the volumetric addition of titra Click n=CV button above EDTA 4+ in the input frame, enter volume and concentration of the titrant used. 243 0 obj <> endobj h, 5>*CJ H*OJ QJ ^J aJ mHsH.h 0000001814 00000 n 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. @ 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* Dissolve the salt completely using distilled or de-ionized water. 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, \[\dfrac{M_\textrm{EDTA}V_\textrm{EDTA}-M_\textrm{Cd}V_\textrm{Cd}}{M_\textrm{Cd}V_\textrm{Cd}}=\dfrac{1}{10}\], \[M_\textrm{EDTA}V_\textrm{EDTA}-M_\textrm{Cd}V_\textrm{Cd}=0.1 \times M_\textrm{Cd}V_\textrm{Cd}\], \[V_\textrm{EDTA}=\dfrac{1.1 \times M_\textrm{Cd}V_\textrm{Cd}}{M_\textrm{EDTA}}=1.1\times V_\textrm{eq}\]. Figure 9.29b shows the pCd after adding 5.00 mL and 10.0 mL of EDTA. the reason for adding Mg-EDTA complex as part of the NH 4 Cl - NH 4 OH system explained in terms of requirement of sufficient inactive Mg2+ ions to provide a sharp colour change at the endpoint. Next, we draw a straight line through each pair of points, extending the line through the vertical line representing the equivalence points volume (Figure 9.29d). Preparation of 0.025M MgSO4.7H2O: Dissolve 0.616 grams of analytic grade magnesium sulfate into a 100 mL volumetric flask. (Assume the moles of EDTA are equal to the moles of MgCO3) Chemistry Reactions in Solution Titration Calculations. 0000031526 00000 n Liebigs titration of CN with Ag+ was successful because they form a single, stable complex of Ag(CN)2, giving a single, easily identified end point. Standardization of EDTA: 20 mL of the standard magnesium sulfate solution is pipetted out into a 250 mL Erlenmeyer flask and diluted to 100 mL . 5CJ OJ QJ ^J aJ #h`. 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 value of Cd2+ depends on the concentration of NH3. last modified on October 27 2022, 21:28:28. B = mg CaCO3 equivalent to 1 ml EDTA Titrant. Aim: Determine the total hardness of given water samples. The highest mean level of calci um was obtained in melon (22 0 mg/100g) followed by water leaf (173 mg/100g), then white beans (152 mg/100g . ! 0000011407 00000 n |" " " " " " " # # # # # >$ {l{]K=/=h0Z CJ OJ QJ ^J aJ h)v CJ OJ QJ ^J aJ #hk hk 5CJ OJ QJ ^J aJ h 5CJ OJ QJ ^J aJ h)v 5CJ OJ QJ ^J aJ hL 5CJ OJ QJ ^J aJ hk CJ OJ QJ ^J aJ hH CJ OJ QJ ^J aJ hlx% CJ OJ QJ ^J aJ hlx% hlx% CJ OJ QJ ^J aJ hlx% hH CJ OJ QJ ^J aJ (h- hH CJ OJ QJ ^J aJ mHsH (hk hk CJ OJ QJ ^J aJ mHsH>$ ?$ % % P OQ fQ mQ nQ R yS zS T T T U U U U U U U U U U !U 8U 9U :U ;U =U ?U @U xj j h7 UmH nH u h? Calcium. In addition, EDTA must compete with NH3 for the Cd2+. 0000024745 00000 n As is the case with acidbase titrations, we estimate the equivalence point of a complexation titration using an experimental end point. 0000000961 00000 n Because Ca2+ forms a stronger complex with EDTA, it displaces Mg2+ from the Mg2+EDTA complex, freeing the Mg2+ to bind with the indicator. A 50.00-mL aliquot of the sample, treated with pyrophosphate to mask the Fe and Cr, required 26.14 mL of 0.05831 M EDTA to reach the murexide end point. A complexometric titration method is proposed to determine magnesium oxide in flyash blended cement. The second titration uses, \[\mathrm{\dfrac{0.05831\;mol\;EDTA}{L}\times0.03543\;L\;EDTA=2.066\times10^{-3}\;mol\;EDTA}\]. In the later case, Ag+ or Hg2+ are suitable titrants. 4 23. If we adjust the pH to 3 we can titrate Ni2+ with EDTA without titrating Ca2+ (Figure 9.34b). HWM6W- ~jgvuR(J0$FC*$8c HJ9b\I_~wfLJlduPl At the end point the color changes from wine red to blue. If desired, calcium could then be estimated by subtracting the magnesium titration (d) from the titration for calcium plus magnesium (a). Complexation titrimetry continues to be listed as a standard method for the determination of hardness, Ca2+, CN, and Cl in waters and wastewaters. It is unfit for drinking, bathing, washing and it also forms scales in A 0.4482-g sample of impure NaCN is titrated with 0.1018 M AgNO3, requiring 39.68 mL to reach the end point. startxref (% w / w) = Volume. In the determination of water hardness, ethylene-diaminetetraacetic acid (EDTA) is used as the titrant that complexes Ca2+ and Mg2+ ions. After the equivalence point the absorbance remains essentially unchanged. Furthermore, lets assume that the titrand is buffered to a pH of 10 with a buffer that is 0.0100 M in NH3. 0000000016 00000 n Hardness of water is a measure of its capacity to precipitate soap, and is caused by the presence of divalent cations of mainly Calcium and Magnesium. Solution for Calculate the % Copper in the alloy using the average titration vallue. 0000002315 00000 n Download determination of magnesium reaction file, open it with the free trial version of the stoichiometry calculator. Now that we know something about EDTAs chemical properties, we are ready to evaluate its usefulness as a titrant. Calcium is determined at pH 12 where magnesium is quantitatively precipitated as the hydroxide and will not react with EDTA. The procedure de-scribed affords a means of rapid analysis. Solving equation 9.11 for [Y4] and substituting into equation 9.10 for the CdY2 formation constant, \[K_\textrm f =\dfrac{[\textrm{CdY}^{2-}]}{[\textrm{Cd}^{2+}]\alpha_{\textrm Y^{4-}}C_\textrm{EDTA}}\], \[K_f'=K_f\times \alpha_{\textrm Y^{4-}}=\dfrac{[\mathrm{CdY^{2-}}]}{[\mathrm{Cd^{2+}}]C_\textrm{EDTA}}\tag{9.12}\]. Next, we draw our axes, placing pCd on the y-axis and the titrants volume on the x-axis. 21 19 \end{align}\], Substituting into equation 9.14 and solving for [Cd2+] gives, \[\dfrac{[\mathrm{CdY^{2-}}]}{C_\textrm{Cd}C_\textrm{EDTA}} = \dfrac{3.13\times10^{-3}\textrm{ M}}{C_\textrm{Cd}(6.25\times10^{-4}\textrm{ M})} = 9.5\times10^{14}\], \[C_\textrm{Cd}=5.4\times10^{-15}\textrm{ M}\], \[[\mathrm{Cd^{2+}}] = \alpha_\mathrm{Cd^{2+}} \times C_\textrm{Cd} = (0.0881)(5.4\times10^{-15}\textrm{ M}) = 4.8\times10^{-16}\textrm{ M}\]. Superimposed on each titration curve is the range of conditions for which the average analyst will observe the end point. seems!to!proceed!slowly!near!the!equivalence!point,!after!each!addition!of! 3. Determination of Permanent hardness Take 100 ml of sample hard water in 250 ml beaker. The most widely used of these new ligandsethylenediaminetetraacetic acid, or EDTAforms strong 1:1 complexes with many metal ions. What is pZn at the equivalence point? Report the weight percents of Ni, Fe, and Cr in the alloy. Reaction taking place during titration is. xref %PDF-1.4 % 0000002437 00000 n Having determined the moles of EDTA reacting with Ni, we can use the second titration to determine the amount of Fe in the sample. Click here to review your answer to this exercise. The titrations end point is signaled by the indicator calmagite. To do so we need to know the shape of a complexometric EDTA titration curve. to the EDTA titration method for the determination of total hardness, based on your past experience with the ETDA method (e.g., in CH 321.) The third step in sketching our titration curve is to add two points after the equivalence point. 0000001156 00000 n The reaction of Mg2+ with EDTA may be expressed as: Mg2+ + H2Y2- = MgY-2 + 2H+ The structure of EDTA and the magnesium-EDTA complex (without the hydrogen atoms) is shown below: The endpoint of the titration is determined by the . You will work in partners as determined by which unknown was chosen. 2ml of serum contains Z mg of calcium. As shown in the following example, we can easily extended this calculation to complexation reactions using other titrants. After the equilibrium point we know the equilibrium concentrations of CdY2- and EDTA. As we add EDTA it reacts first with free metal ions, and then displaces the indicator from MInn. Dilute to about 100mL with distilled water. Sketch titration curves for the titration of 50.0 mL of 5.00103 M Cd2+ with 0.0100 M EDTA (a) at a pH of 10 and (b) at a pH of 7. As we add EDTA, however, the reaction, \[\mathrm{Cu(NH_3)_4^{2+}}(aq)+\textrm Y^{4-}(aq)\rightarrow\textrm{CuY}^{2-}(aq)+4\mathrm{NH_3}(aq)\], decreases the concentration of Cu(NH3)42+ and decreases the absorbance until we reach the equivalence point. The blue line shows the complete titration curve. Note that the titration curves y-axis is not the actual absorbance, A, but a corrected absorbance, Acorr, \[A_\textrm{corr}=A\times\dfrac{V_\textrm{EDTA}+V_\textrm{Cu}}{V_\textrm{Cu}}\]. $d 7$ 8$ H$ a$gd, d 7$ 8$ H$ gd% | ~ zhY h, 5CJ OJ QJ ^J aJ #h, h, 5CJ OJ QJ ^J aJ #h, h% 5CJ OJ QJ ^J aJ +h;- h, 5CJ OJ QJ ^J aJ mHsH.h;- h% 5CJ H*OJ QJ ^J aJ mHsH +h;- h% 5CJ OJ QJ ^J aJ mHsH.h;- h, 5CJ H*OJ QJ ^J aJ mHsH .h;- h% 5CJ H*OJ QJ ^J aJ mHsH q t xcM8 (h, h% CJ# OJ QJ ^J aJ# mHsH +h
Falling Away Scripture Kjv,
Police Academy Running Cadence,
Articles D