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Calculate pCu2+ at each of the following points in the titration of 50.00 mL of 0.001 00 M Cu2+ with 0.00100 M EDTA at pH 11.00 in a solution with [NH3] fixed at 1.00 M:

(a) 0 mL(b) 1.00 mL (c) 45.00 mL (d) 50.00 mL (e) 55.00 mL

Short Answer

Expert verified

(e) For 55 mL the value ofpCu2+is 17.69.

Step by step solution

01

Introduction

Equations and data obtained in order to proceed for calculation are as follows

Cu2++Y4CuY2Kf=1018.78=6.03×1018At   pH   11   αY4=0.81Table121logβ1=3.99logβ2=7.33logβ3=10.06logβ4=12.03

The beta(β) values were obtained from appendix-1 for Cu2+ and NH3

02

Determine equilibrium constant

αCu2+=11+β11.00+β21.002+β31.003+β41.004=9.23×1013Kf'=αY4Kf=0.81×6.03×1018=4.88×1018Kf"=αCu2+×Kf'=9.23×1013×4.88×1018

Equivalence point=50 mL

03

Determine the value of pCu2+

Past equivalence point (55mL) we can calculate

EDTA=5105×0.001M=4.76×105MCuY2=50105×0.001M=4.76×104M

Kf'=CuY2Cu2+EDTA4.88×1018=4.76×104Cu2+4.76×105Cu2+=2.05×1018M

Therefore, the value of pCu2+

pCu2+=logCu2+=log2.05×1018=17.69

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Most popular questions from this chapter

Consider the titration of 25.0 mL of 0.020 0 M MnSO4 with 0.010 0 M EDTA in a solution buffered to pH 8.00. Calculate pMn2+ at the following volumes of added EDTA and sketch the titration curve:

(a) 0 mL (b) 20.0 mL (c) 40.0 mL (d) 49.0 mL (e) 49.9 mL (f) 50.0 mL (g) 50.1 mL

(h) 55.0 mL (i) 60.0 mL

Spreadsheet equation for formation of the complexes ML and ML2.Consider the titration of metal M (initial concentration = CM, initial volume = VM) with ligand L (concentration = CL, volume added = VL), which can form 1:1 and 2 : 1 complexes:

M+L𝆏MLβ1=[ML][M][L]M+2L𝆏ML2β2=[ML2][M][L]2

Let αM be the fraction of metal in the form M, αML be the fraction in the form ML, and αML2be the fraction in the form ML2. Following the derivation in Section 12-5, you could show that these fractions are given by

role="math" localid="1667801924683" αM1=11+β1[L]+β2[L]2αML=β1[L]1+β1[L]+β2[L]2αML2=β2[L]21+β1[L]+β2[L]2

The concentrations of ML and ML2are

[ML]=αMLCMVMVM+VL[ML2]=αML2CMVMVM+VL

because CMVMVM+VLis the total concentration of all metal in the solution. The mass balance for ligand is

[L]+[ML]+2[ML2]=CMVMVM+VL

By substituting expressions for [ML] and [ML2] into the mass balance, show that the master equation for a titration of metal by ligand is

ϕ=CLVLVM+VM=αML+2αML2+LCM1-LCL

Spreadsheet equation for auxiliary complexing agent. Consider the titration of metal M (initial concentration = CM, initial volume = VM) with EDTA (concentration = CEDTA, volume added = VEDTA) in the presence of an auxiliary complexing ligand (such as ammonia). Follow the derivation in Section 12-4 to show that the master equation for the titration is

ϕ=CEDTAVEDTACMVM=1+Kf′′[M]free[M]free+Kf′′[M]freeCMKf′′[M]free+[M]free+Kf′′[M]free2CEDTA

where Kf''is the conditional formation constant in the presence of auxiliary complexing agent at the fixed pH of the titration (Equation 12-18) and [M]free is the total concentration of metal not bound to EDTA. [M]free is the same as [M] in Equation 12-15. The result is equivalent to Equation 12-11, with [M] replaced by [M]free andKfreplaced by Kf''.

According to Appendix I, Cu2+ forms two complexes with acetate:

Cu2++CH3CO2Cu(CH3CO2)+       β1(=K1)Cu2++2CH3CO2Cu(CH3CO2)2       β2

(a) Referring to Box 6-2, find K2 for the reaction

Cu(CH3CO2)++CH3CO2Cu(CH3CO2)2(aq)   K2

(b) Consider 1.00 L of solution prepared by mixing 1.00 × 10-4 mol Cu(ClO4)2 and 0.100 mol CH3CO2Na. Use Equation 12-16 to find the fraction of copper in the form Cu2+


Consider the titration of 25.0 mL of 0.020 0 M MnSO4 with 0.010 0 M EDTA in a solution buffered to pH 8.00. Calculate pMn2+ at the following volumes of added EDTA and sketch the titration curve:

(a) 0 mL (b) 20.0 mL (c) 40.0 mL (d) 49.0 mL (e) 49.9 mL (f) 50.0 mL (g) 50.1 mL(h) 55.0 mL (i) 60.0 mL

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