VNU- HUS- Analytical chemistry- Spring 2020 Homework assignments –

Lecture 4 (Chemical Equilibria)

(Find more exercises in the book: D. Harvey, Modern analytical chemistry, McGraw Hill Higher
Education, 2000)
Note: Ka, Kf, Ksp; E0 are drawn from booklets.

1. Acid- base equilibrium

Problem 1: Calculate the pH of
a- 1.0x10-8 HBr
b- A solution prepared by dissolving 1.23 g of 2- nitrophenol ( FM 139.11) in 0.250 L.
c- A 0.050 M sodium butanoate.
Problem 2: A solution contains 63 different conjugate acid- base pairs. Among them is acrylic
acid and acrylate ion, with the equilibrium ratio [acrylate]/[acrylic acid]= 0.75. What is pH of the
solution.
Problem 3: Find the pH and concentrations of (CH3)3,N and (CH3)3NH+ in a 0.060 M solution of
trimethylamine.
Problem 4: Which of the following acids would be most suitable for preparing a buffer of pH
3.10: (i) hydrogen peroxide; (ii) propanoic acid; (iii) cyanoacetic acid; (iv) 4-
aminobenzenesulfonic acid?
Problem 5: A buffer was prepared by dissolving 0.100 mol of the weak acid HA (Ka = 1.00 X 10-
5
) plus 0.050 mol of its conjugate base Na+A- in 1.00 L. Find the pH.
Problem 6: Consider the diprotic acid H2A with K1 = 1.00 X 10-4 and K2 = 1.00 X l0-8. Find the pH
and concentrations of H2A, HA-, and A2- in
(a) 0.100 M H2A;
(b) 0.100 M NaHA;
(c) 0.100 M Na2A.
Problem 7: How many milliliters of 0.202 M NaOH should be added to 25.0 mL of 0.0233 M
salicylic acid (2-hydroxybenzoic acid) to adjust the pH to 3.50?
Problem 8: a) Which two of the following compounds would you mix to make a buffer of pH
7.45: H3PO4, (FM 98.00), NaH2PO4 (FM 119.98), Na2HPO4 (FM 141.96), and Na3PO4 (FM
163.94)?
(b) If you wanted to prepare 1.00 L of buffer with a total phosphate concentration of 0.0500 M,
how many grams of each of the two selected compounds would you mix together?
(c) If you did what you calculated in part (b), you would not get a pH of exactly 7.45. Explain
how you would really prepare this buffer in the lab.
2. Complexon equilibrium
Problem 9: Consider the reactions of Fe2+ with the amino acid glycine:

Fe2+ + G-  FeG+ log1= 4.31

Fe2+ + 2G-  FeG2(aq) log2= 7.65 = log (Kf1xKf2)

Fe2+ + 3G-  FeG3-; log3= 8.87=log (Kf1xKf2xKf3)

1
Fe2+ + H20  FeOH+ + H+ pKa = 9.4 or logKf*= - (14-9.4)= - 4.6

H3NCH2CO2H glycine, H2G+ pK1 = 2.350, pK2 = 9.778

+

Suppose that 0.050 mol of FeG2 is dissolved in 1.00 L and enough HCl is added to adjust the pH
to 8.50. Find the composition of the solution. What fraction of iron is in each of its forms and
what fraction of glycine is in each of its forms?

3.Precipitation equilibrium
Problem 10: a) Find the concentration of Cu+ in equilibrium with CuBr(s) and 0.10M Br-
b) Find [Cu2+] in a solution saturated with Cu4(OH)6(SO4) if [OH-] is fixed at 1.0 X l0-5 M.
Note that Cu4(OH)6(SO4) gives 1 mol of SO42- for 4 mol of Cu2+.
Cu4(OH)6(SO4)(s)  4Cu2+ + 60H- + S042- Ksp = 2.3 X 10-69
Problem 11: The planet Aragonose (which is made mostly of the mineral aragonite, whose
composition is CaCO3) has an atmosphere containing methane and carbon dioxide, each at a
pressure of 0.10 bar.
The oceans are saturated with aragonite and have a concentration of H+ equal to 1.8 X l0-7 M.
Given the following equilibria, calculate how many grams of calcium are contained in 2.00 L of
Aragonose seawater.
CaCO3(s,aragonite)  Ca2+(aq) + CO32-(aq) Ksp = 6.0 X l0-9
C02(g) 3 CO2 (aq) KC02= 3.4 x 10-2
CO2(aq) + H2O(l) HCO3-(aq) + H+(aq) K1 = 4.5 x 10-7
HCO3-(aq)  H+ (aq) + CO32- (aq) K2= 4.7x10-11
4. Redox equilibrium
Problem 12: a) Calculate the conditional standard potential of Cu2+Cu+ in the present of KCN
0.025 M.
b) Calculate the conditional standard potential of Fe3+/Fe2+ in a solution containing 2.00 mmol
of Fe(NH4)2(SO4)2, 1.00 mmol of FeCl3, 4.00 mmol of Na2H2Y and lots of buffer, pH 6.78, in a
volume of 1.00 L.
c) Calculate the conditional standard potential of Ni3+/Ni2+ in a NH4+/ NH3 buffer of pH 9.