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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

=CETDAVETDACMVM=1+Kf"[M]free-[M]free+Kf"[M]freeCMKf"[M]free+[M]free+Kf"[M]free2CETDA

where role="math"> 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 and Kf replaced by Kf".

Short Answer

Expert verified

The following master equation for titration is derived

=CETDAVETDACMVM=1+Kf"[M]free-[M]free+Kf"[M]freeCMKf"[M]free+[M]free+Kf"[M]free2CETDA

Step by step solution

01

Reaction involved

The following equation can be written in place of 12-8

Mfree+ETDA饾啅METDA

The equilibrium constant can be written as

Kf"=METDAMfreeETDA---------------1Mfree=ConcentrationofallmetalsnotboundtoETDAETDA=ConcentrationofallETDAnotboundtometalsMETDA=KF"MfreeETDA--------------2

02

Mass Balance

Mass balance for metal: Mfree+MEDTA=CMVMVM+VEDTA-----------3

Mass balance for EDTA: ETDA+MEDTA=CEDTAVEDTAVMVEDTA----------4

03

Derivation

Substituting Eq (2) into Eq (3) we get

[M]Free+Kf[M]ree[EDTA]=CMVMVM+VEDTA[M]Free1+Kf鈥测赌[EDTA]=CMVMVM+VEDTA-----------5

Substituting Eq (2) into Eq (4) we get

[EDTA]+Kf[M]free[EDTA]=CEDTAVEDTAVM+VEDTA[EDTA]1+Kf[M]fee=CEDTAVEDTAVM+VEDTA[EDTA]=CEDTAVEDTAVM+VEDTA1+Kf[M]free------------6

Substituting Eq(6) into Eq (5)

[M]Free1+KfCEDTAVEDTAVM+VEDTA1+Kf[M]tee=CMVMVM+VEDTA[M]Free1+Kf[M]feeVM+VEDTA+KiCEDTAVEDTA1+Kf[M]freeVM+VEDTA=CMVMVM+VEDTA1[M]Free1+Kf[M]treeCEDTAVEDTA1+Kf[M]teeVM+VEDTA+KfCEDTAVEDTA=CEDTAVEDTACMVM1+Kf[M]ree[M]tree+Kf[M]reeCMKf[M]free+[M]tee+Kf[M]free2CEDTA=CEDTAVEDTACMVM1+Kf[M]tee[M]free+Kf[M]feeCMKf[M]free+[M]tee+Kf[M]fee2CEDTA=

Therefore, the expression given in the question is proved.

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Most popular questions from this chapter

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

Calcium ion was titrated with EDTA at pH 11, using Calmagite as indicator (Table 12-3). Which is the principal species of Calmagite at pH 11? What color was observed before the equivalence point? After the equivalence point?

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饾啅ML1=[ML][M][L]M+2L饾啅ML22=[ML2][M][L]2

Let 伪M be the fraction of metal in the form M, 伪ML be the fraction in the form ML, and ML2be 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" M1=11+1[L]+2[L]2ML=1[L]1+1[L]+2[L]2ML2=2[L]21+1[L]+2[L]2

The concentrations of ML and ML2are

[ML]=MLCMVMVM+VL[ML2]=ML2CMVMVM+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

=CLVLVM+VM=ML+2ML2+LCM1-LCL

Calculate the concentration of H2Y2- at the equivalence point in Exercise 12-C

Find [Ca2+] in 0.10 M CaY2- at pH 8.00

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