USTH- Analytical chemistry- Fall 2013 Homework assignments –

Lecture 5: Volumetric titration.

(for 2nd BP and WEO students)

(Find more exercises in the book: D. Harvey, Modern analytical chemistry, McGraw Hill
Higher Education, 2000)

Problem 1: Tartaric acid, H2C4H4O6, is a diprotic weak acid with a pKa1 of 3.0 and a pKa2
of 4.4. Suppose you have a sample of impure tartaric acid (%purity > 80) and that you
plan to determine its purity by titrating with a solution of 0.1 M NaOH using a visual
indicator to signal the end point.
Describe how you would carry out the analysis, paying particular attention to how much
sample you would use, the desired pH range over which you would like the visual
indicator to operate, and how you would calculate the %w/w tartaric acid.
Problem 2: For each of the following, determine the forms of alkalinity (OH–, HCO3–,
CO32–) that are present, and their respective concentrations in parts per million. In each
case, a 25.00-mL sample is titrated with 0.1198 M HCl to the bromocresol green and
phenolphthalein end points.
Volume of HCl (mL) to Volume of HCl (mL)
the Phenolphthalein End Point to the Bromocresol Green End Point
(a) 21.36 21.38
(b) 5.67 21.13
(c) 0.00 14.28
(d) 17.12 34.26
(e) 21.36 25.69
Problem 3: The concentration of CO2 in air can be determined by an indirect acid–base
titration. A sample of the air is bubbled through a solution containing an excess of
Ba(OH)2, precipitating BaCO3. The excess Ba(OH)2 is back titrated with HCl. In a typical
analysis, a 3.5-L sample of air was bubbled through 50.00 mL of 0.0200 M Ba(OH)2.
Back titrating with 0.0316 M HCl requires 38.58 mL to reach the end point. Determine
the parts per million of CO2 in the sample of air, given that the density of CO2 at the
temperature of the sample is 1.98 g/L.
Problem 4: Calculate or sketch (or both) the titration curves for 50.00 mL of 0.0500 Mg2+
with 0.0500 M EDTA at a pH of 7 and 10. Locate the equivalence point for each titration
curve.
Problem 5: A cyanide solution with a volume of 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-
The excess Ni2+ was then titrated with 10.15 ml. of 0.01307 M ethylenediaminetetraacetic
acid (EDTA):
Ni2+ + EDTA4- Ni(EDTA)2-
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
cyanide sample.
Problem 6: Consider the titration of 25.00 mL of 0.082 30 M KI with 0.05110 M
AgNO3. Calculate pAg at the following volumes of added AgNO3: (a) 39.00 mL; (b) Ve;
(c) 44.30 mL.
Problem 7: A 0.2386 -g sample contained only NaCl and KBr. It was dissolved in water
and required 48.40 mL of 0.04837 M AgNO3 for complete titration of both halides
[giving AgCl(s) and AgBr(s)]. Calculate the weight percent of Br in the solid sample.
Problem 8 : A 50.0-mL sample of 0.080 0 M KSCN is titrated with 0.0400 M Cu+. The
solubility product of CuSCN is 4.8 x 1014.
At each of the following volumes of titrant, calculate pCu, and construct a graph of pCu+
versus milliliters of Cu+ added: 0.10, 10.0, 25.0, 50.0, 75.0, 95.0, 99.0, 100.0, 100.1,
101.0, 110.0 mL.
Consider the titration of 50.00 (0.05) mL of a mixture of I- and SCN- with 0.0683
(0.000 1) M Ag+. The first equivalence point is observed at 12.6 (0.4) mL, and the
second occurs at 27.7 (0.3) mL.
(a) Find the molarity and the uncertainty in molarity of thiocyanate in the original
mixture.
(b) Suppose that the uncertainties are all the same, except that the uncertainty of the first
equivalence point (12.6  0.2 mL) is variable.
What is the maximum uncertainty (milliliters) of the first equivalence point if the
uncertainty in SCN- molarity is to be 54.0%?

Problem 9: A redox buffer contains an oxidizing agent and its conjugate reducing agent.
Calculate the potential of a solution containing 0.010 mol of Fe3+ and 0.015 mol of Fe2+.
What is the potential if sufficient oxidizing agent is added such that 0.002 mol of Fe2+ is
converted to Fe3+?

Problem 10: Arsenic(III) oxide (As203) is available in pure form and is a useful (but
carcinogenic) primary standard for oxidizing agents such as MnO4-. The As2O3 is
dissolved in base and then titrated with MnO4- in acidic solution. A small amount of
iodide (I-) or iodate (IO3-) is used to catalyze the reaction between H3AsO3 and
MnO4-.
As2O3 + 4OH-  2HAsO32- + H2O
HAsO32+ 2H+  H3AsO3
5H3AsO3 + 2MnO4- + 6H+ —> 5H3AsO4 + 2Mn2+ + 3H2O

(a) 3.214-g aliquot of KMnO4 (FM 158.034) was dissolved in 1.000 L of water, heated to
cause any reactions with impurities to occur, cooled, and filtered. What is the theoretical
molarity of this solution if no MnO4-; was consumed by impurities?
(b) What mass of As203 (FM 197.84) would be just sufficient to react with 25.00 mL of
the KMnO4 solution in part (a)?
(c) It was found that 0.146 8 g of As2O3 required 29.98 mL of KMnO4 solution for the
faint color of unreacted MnO4-; to appear. In a blank titration, 0.03 mL of MnO4- was
required to produce enough color to be seen. Calculate the molarity of the permanganate
solution.

Problem 11: The concentration of cyanide, CN– , in a copper electroplating bath can be
determined by a complexometric titration with Ag+ , forming the soluble Ag(CN)2 –
complex. In a typical analysis a 5.00-mL sample from an electroplating bath is
transferred to a 250-mL Erlenmeyer flask, and treated with 100 mL of H2O, 5 mL of 20%
w/v NaOH, and 5 mL of 10% w/v KI. The sample is titrated with 0.1012 M AgNO3,
requiring 27.36 mL to reach the end point as signaled by the formation of a yellow
precipitate of AgI. Report the concentration of cyanide as parts per million of NaCN.
The level of dissolved oxygen in a water sample can be determined by the Winkler
method. In a typical analysis, a 100.0-mL sample is made basic, and treated with a
solution of MnSO4, resulting in the formation of MnO2. An excess of KI is added, and
the solution is acidified, resulting in the formation of Mn2+ and I2. The liberated I2 is
titrated with a solution of 0.00870 M Na2S2O3, requiring 8.90 mL to reach the starch
indicator end point. Calculate the concentration of dissolved oxygen as parts per million
of O2.