Họ và tên : Vũ Huyền Thương

Lớp : K63D1- Hóa dược

HOMEWORK 8
11-C. Calculate pCu2+ (to the 0.01 decimal place) at each of the following points in
the titration of 50.0 mL of 0.040 0 M EDTA with 0.080 0 M Cu(NO3)2 at pH 5.00:
0.1, 5.0, 10.0, 15.0, 20.0, 24.0, 25.0, 26.0, and 30.0 mL. Make a graph of pCu2+
versus volume of titrant.

Kf’ = Kf.αY4- = 1018.78×2.9×10-7 = 1.75×1012

V= 0.1 ml

V=5.0 ml

V=10.0 ml

V=20.0 ml
V=24.0 ml

V=25.0 ml =Veq

Cu2+ + EDTA → CuY2-

x x 2.67×10-2 - x

V=26.0 ml

V=30 ml
 16

14

12

10
pCu2+

0
0 5 10 15 20 25 30 35

VCu2+ (ml)

11-F. A solution containing 20.0 mL of 1.00× 10-3 M Co2+ in the presence of 0.10M
C2O42- at pH 9.00 was titrated with 1.00× 10-2 M EDTA. Using formation constants
from Appendix I for Co(C2O4) and Co(C2O4)22-, calculate pCo2+ for the following
volumes of added EDTA: 0, 1.00, 2.00, and 3.00 mL. Consider the concentration of
C2O42- to be fixed at 0.10 M. Sketch a graph of pCo2+ versus milliliters of added
EDTA

V=0 ml
[Co2+] =αCo2+.CCo2+ =6.84×10-6×1.00× 10-3 =6.84×10-9 M ⇒pCo2+ =8.16
V=1.00 ml

V= 2.00 ml = Veq

CCo2+ + EDTA → CoY2-

x x 9.09× 10-4 - x

V=3.00 ml
 16
14
12
10
pCo2+

8
6
4
2
0
0 0.5 1 1.5 2 2.5 3 3.5
VEDTA(ml)

11-26. Pyrocatechol violet (Table 11-3) is to be used as a metal ion indicator in an

EDTA titration. The procedure is as follows:
1. Add a known excess of EDTA to the unknown metal ion.
2. Adjust the pH with a suitable buffer.
3. Back-titrate the excess chelate with standard Al3. From the following available
buffers, select the best buffer, and then state what color change will be observed at the
end point. Explain your answer.
(a) pH 6–7 (b) pH 7–8 (c) pH 8–9 (d) pH 9-10
I chose buffer (a)
Because in the buffer (a) : yellow →blue
in the buffer (b) ,(c ), (d) : violet →blue , which is harder see
11-34. Cyanide solution (12.73 mL) was treated with 25.00 mL of Ni2+ solution
(containing excess Ni2+) to convert the cyanide into tetracyanonickelate(II):
4CN- + Ni2+ → Ni(CN)42-
Excess Ni2+ was then titrated with 10.15 mL of 0.013 07 M EDTA. Ni(CN)42-
does not react with EDTA. If 39.35 mL of EDTA were required to react with 30.10
-
mL of the original Ni2+ solution, calculate the molarity of CN in the 12.73-mL
sample.
Ni2+ + EDTA → NiY2-

The moles of Ni2+ in 25.00 ml of Ni2+ solution

 nNi2+ = 0.01709×25.00×10-3 =4.2716×10-4 (mol)
The moles of Ni2+ react with EDTA
nNi2+ = nEDTA= 10.15×10-3×0.01307 = 1.3266×10-4 (mol)
The moles of Ni2+ react with CN- :
nNi2+= 4.2716×10-4 - 1.3266×10-4 =2.9450×10-4 (mol)
nCN- =4nNi2+= 4×2.9450×10-4 = 1.1780×10-3 (mol)
-
The molarity of CN in the 12.73-mL sample

11-38. Indirect EDTA determination of cesium. Cesium ion does not form a strong
EDTA complex, but it can be analyzed by adding a known excess of NaBiI4 in cold
concentrated acetic acid containing excess NaI. Solid Cs3Bi2I9 is precipitated,
-
fifiltered, and removed. The excess yellow BiI4 is then titrated with EDTA. The end
point occurs when the yellow color disappears. (Sodium thiosulfate is used in the
reaction to prevent the liberated I- from being oxidized to yellow aqueous I2 by O2
from the air.) The precipitation is fairly selective for Cs. The ions Li, Na, K, and low
concentrations of Rb do not interfere, although Tl does. Suppose that 25.00 mL
of unknown containing Cs were treated with 25.00 mL of 0.086 40 M NaBiI4 and the
-
unreacted BiI4 equired 14.24 mL of 0.043 7 M EDTA for complete titration. Find the
concentration of Cs in the unknown.

nNaBiI4 = 0.086 40×25.00×10-3 = 2.160×10-3 (mol)

nEDTA = 0.043 7×14.24 ×10-3 = 6.223×10-4 (mol)
nNaBiI4(excess ) = 2.160×10-3 - 6.223×10-4 = 1.538×10-3 (mol)
2NaBiI4 + 3Cs + NaI → Cs3Bi2I9 + 3Na

Solutions containing both Fe3+ and Al3+ can be selectively analyzed for Fe3+ by
bufering to a pH of 2 and titrating with EDTA. The pH of the solution is then
raised to 5 and an excess of EDTA added, resulting in the formation of the Al3+
–EDTA complex. The excess EDTA is back-titrated using a standard solution of
Fe3+, providing an indirect analysis for Al3+.
(a) At a pH of 2, verify that the formation of the Fe3+–EDTA complex is favorable,
and that the formation of the Al3+–EDTA complex is not favorable.
(b) A 50.00-mL aliquot of a sample containing Fe3+ and Al3+ is transferred to
a 250-mL Erlenmeyer flask and bufered to a pH of 2. A small
amount of salicylic acid is added, forming the soluble red-colored Fe3+–
salicylic acid complex. The solution is titrated with 0.05002 M EDTA, requiring
24.82 mL to reach the end point as signaled by the disappearance of the Fe3+–
 salicylic acid complex’s red color. The solution is bufered to a pH of 5 and
50.00 mL of 0.05002 M EDTA is added.
(c) After ensuring that the formation of the Al3+–EDTA complex is
complete, the excess EDTA was back titrated with 0.04109 M Fe3+, requiring
17.84 mL to reach the end point as signaled by the reappearance of the red-
colored Fe3+-salicylic acid complex. Report the molar concentrations of Fe3+ and
Al3+ in the sample.