Chem 28 Complex Formation 17-20.
Given:
y y y y y
EDTA soln prepared by 4.0 gram disodium salt dissolved in 1 liter water Average of 42.35 mL req to titrate 50.0 mL aliq of 0.7682 g MgCO3/L std. Titration of 25 mL mineral water at pH 10 req 18.81 mL of EDTA. A 50 mL aliq of mineral water (made alkaline to ppt Mg as Mg(OH)2 and w/ Ca-spec indicat) req 31.54 mL EDTA soln. Calc a) Molarity of EDTA soln. (b) conc(ppm) of CaCO3 in water (c) conc (ppm) of MgCO3
Solution: a) Approx conc. = M EDTA = V x M EDTA = = 0.010746 mole/liter
Standard conc: mmole EDTA = mmole MgCO3
0.04235 L x M = = M=
= 4.56 x 10-4 mole
= 0.010757 M
b) mmole CaCO3 = mmole EDTA (w/ Mg)
= 18.81 mL EDTA x 0.010757 mmol/mL
wt CaCO3 (mg) = 20.25 mg (in 25 mL water sample)
ppm CaCO3 =
= 810 mg/L (ppm)
c) mmole CaCO3 = mmole EDTA (w/o Mg) wt CaCO3 (mg) = 31.54 mL x 0.010757 mmol/mL x 100.087 mg/mmol = 33.9571 mg (in 50 mL water sample) ppm CaCO3 = = = 679.14 mg/L (ppm) as CaCO3
y y y
(CaCO3 + MgCO3) - CaCO3 810 mg/L 679.14 mg/L = 130.96 mg/L CaCO3 130.96 mg/L CaCO3 x
= 110.322 mg/L MgCO3
17.25. Given:
y y y y y y
Calamine = mixture of Zn and Fe oxides 1.022 g calamine dissolved in acid and diluted to 250 mL KF was added to 10 mL aliq to mask the Fe After adjustment of pH, titration of Zn 2+ consumed 38.71 mL (0.01294 M) EDTA A 2nd aliq 50 mL, added w/ buffer and titrated, consumed 2.4 mL (0.002727 M ) ZnY 2- solution Calculate % ZnO and % Fe2O3 in the sample Fe3+ + ZnY2FeY- + Zn 2+
Solution: mmole Zn = mmole EDTA mg Zn = 38.71 mL x 0.01294 mmol/mL x 65.409 mg Zn/mmol = 32.7639 mg Zn in 10 mL aliquot mg Zn = 32.7639 mg x
= 819.096 mg Zn
mg ZnO = 819.096 mg Zn x
= 1019.4464 mg ZnO
% ZnO =
x 100 = 99.75%
mmole Fe = mmole EDTA mg Fe = 2.4 mL x 0.002727 mmol/mL x 55.845 mg Fe/mmol = 0.3655 mg Fe in 50 mL aliquot mg Fe= 0.3655 mg Fe x
= 1.8275 mg Fe
mg Fe2O3 = 1.8275 mg Fe x mg Fe2O3 = 1.8275 mg Fe x
= 2.6128 mg
% Fe2O3 =
x 100 = 0.25%
17-29. Given:
y y y y y y
0.3284 gram Brass sample (containing Pb, Zn, Cu, Sn) dissolved in HNO3 SnO2.4H2O was removed by filtration, filtrate was diluted to 500 mL 10 mL aliq + buffer, for titration of (Pb, Zn, Cu) required 37.56 mL (0.0025 M) EDTA In a 25 mL aliquot, Cu was masked w/ thiosulfate, then Pb and Zn were titrated with 27.67 mL EDTA. In another 100 mL aliquot, CN- ion was used to mask the Cu +Zn; and titration of Pb required 10.80 mL EDTA Determine composition of the brass sample; evaluate % Sn by difference.
Solution: Conc of Pb, Zn, Cu in 10 mL aliquot = 37.56 mL x 0.0025 mmol/mL x Conc of Pb, Zn in 25 mL aliquot = 27.67mL x 0.0025 mmol/mL x
= 4.695 mmol
= 1.39 mmol
= 0.135 mmol Conc of Pb in 100 mL aliquot = 10.8 mL x 0.0025 mmol/mL x --------------mg Cu = [4.695 mmol 1.39 mmol] x 63.546 mg Cu/mmol = 210.02 mg Cu
% Cu = ----------------
x 100 = 63.95%
mg Zn = [1.39 mmol 0.135 mmol] x 65.409 mg Zn/mmol = 82.088 mg Zn
% Zn =
x 100 = 24.996%
--------------mg Pb = 0.135 mmol x 207.2 mg/mmol = 27.922 mg Pb % Pb =
x 100 = 8.50%
--------------% Sn = 100% - [65.409 24.996 + 8.50]% = 2.554% Sn
17.32 Titration Curve Derive a titration curve for 50 mL (0.01M) Sr2+ w/ 0.02M EDTA in a solution buffered to pH 11.0 Calculate p Sr values after addition of 0.0 mL, 10.0 mL, 24.0 mL, 24.9 mL, 25.0 mL, 25.1 mL, 26.0 mL, and 30.0 mL EDTA
Solution: K SrY = 4.3 x 108 KSrY = 4 K SrY ; [ 4 EDTA at pH 11 = 0.85] KSrY = 0.85 (4.3 x 108) = 3.655 x 108 *At Initial pt and pre-equiv pt, pSr are computed from equil conc. At 0.0 mL EDTA added, [Sr2+] = At 10.0 mL EDTA added, [Sr2+] = At 24.0 mL EDTA added, [Sr2+] = At 24.9 mL EDTA added, [Sr2+] =
1 x 10-2 M
pSr = 2.0 5 x 10-3 M 2.7 x 10-4 M 2.67 x 10-5 M pSr = 2.3 pSr = 3.6 pSr = 4.6
*At Equivalence Point ,
Sr2+ + Y 4-
[Sr2+] is computed based on
; [Sr2+ ] = [Y4-] ;
SrY2- ; KSrY = 3.655 x 108; KSrY =
[Sr2+ ]2 =
[Sr2+ ]2 =
At 25.0 mL EDTA added, ;
= 4.27 x 10 -6
pSr = 5.37
*At Post- Equivalence Point ,
Calculation of Sr2+ required the equation KSrY = KSrY =
; KSrY =
KSrY; [Y4-] =
4 CT
[Sr2+ ] = [Sr2+ ] = [Sr2+ ] = [Sr2+ ] =
At 25.1 mL EDTA added; At 26.0 mL EDTA added; At 30.0 mL EDTA added;
= 7.01 x 10-7 = 6.83 x 10-8 = 1.37 x 10-8
pSr = 6.15 pSr = 7.16 pSr = 7.86
Titration curve (Complex formation)
Titration Curve (Sr and EDTA)
9.00
8.00 7.16
7.86
7.00
6.00
6.15 5.37
5.00
pSr
4.00
4.60
3.60 3.00 2.30 2.00
1.00
0.00 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0
Volume (mL) EDTA
