Ho Chi Minh City University of Technology

Department of Physicochemical & Analytical Technologies

Bài tập Hoá lý 2 (Physical Chemistry 2 - Homework)

Part 1. Electrochemistry

Data: Equivalent conductivities of ions in water at 25 oC (using for exercises)

5.18(b) Calculate the ionic strength of a solution that is 0.040 mol kg−1 in K3[Fe(CN)6](aq), 0.030 mol kg−1 in KCl(aq),
and 0.050 mol kg−1 in NaBr(aq).
0.320
5.19(b) Calculate the masses of (a) KNO3 and, separately, (b) Ba(NO3)2 to add to a 0.110 mol kg−1 solution of KNO3(aq)
containing 500 g of solvent to raise its ionic strength to 1.00.
(a) 45.0 kg KNO3; (b) 38.8 g Ba(NO3)2.
5.20(b) Estimate the mean ionic activity coefficient and activity of a solution that is 0.020 mol kg−1 NaCl(aq) and 0.035
mol kg−1 Ca(NO3)2(aq).
For NaCl,  = 0.661
25.21b A 0.10 M FeSO4(aq) solution is electrolysed between a magnesium cathode and a platinum anode with a current
density of 1.50 mA cm−2. The hydrogen overpotential is 0.60 V. What will be the concentration of Fe 2+ ions when
evolution of H2 just begins at the cathode? Assume all activity coefficients are unity.
[Fe2+] = 4 × 10−6 mol dm−3
25.32b The corrosion current density icorr at a zinc anode is 2.0 A m−2. What is the corrosion rate in millimetres per year?
Assume uniform corrosion, Zn (M = 65.4 g/mol, d = 7.14 g/cm3)
3.0 mm/yr
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Department of Physicochemical & Analytical Technologies

Answer:
10.35 0.330 mol/kg
15.39 (a) T; (b) T; (c) F; (d) F; (e) T. 15.40 1.19 g.
15.41 (c) 472.21 cm2 -1 mol-1.
15.42 (a) 248.4 cm2 -1 mol-1; (b) 124.2 cm2 -1 equiv-1.
15.45 t- = 0.4883
15.46 (a) 100.4 cm2 -1 mol-1; (b) 391 cm2 -1 mol-1.
15.60 1.74 x 10-5
Other questions don’t have answers
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies

Answer:

Note: questions 13.44 to 13.46 don’t have answers

 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies

Part 2. Surface phenomena

25.4b A monolayer of CO molecules (effective area 0.165 nm2) is adsorbed on the surface of 1.00 g of an Fe/Al 2O3 catalyst at 77 K,
the boiling point of liquid nitrogen. Upon warming, the carbon monoxide occupies 4.25 cm 3 at 0°C and 1.00 bar. What is the surface
area of the catalyst?
A = 18.8 m2

25.9b A certain solid sample adsorbs 0.63 mg of CO when the pressure of the gas is 36.0 kPa and the temperature is 300 K. The mass
of gas adsorbed when the pressure is 4.0 kPa and the temperature is 300 K is 0.21 mg. The Langmuir isotherm is known to describe
the adsorption. Find the fractional coverage of the surface at the two pressures.
θ1 = 0.75, θ2 = 0.25

25.4 The data below are for the chemisorption of hydrogen on copper powder at 25°C. Confirm that they fit the Langmuir isotherm
at low coverages. Then find the value of K for the adsorption equilibrium and the adsorption volume corresponding to complete
coverage.

p/Pa 25 129 253 540 1000 1593

V/cm3 0.042 0.163 0.221 0.321 0.411 0.471

K = 0.0028 Pa-1

25.5 The data for the adsorption of ammonia on barium fluoride are reported below. Confirm that they fit a BET isotherm and find
values of C* and Vm.
(a) θ = 0°C, Po = 429.6 kPa:

p/kPa 14.0 37.6 65.6 79.2 82.7 100.7 106.4

V/cm3 11.1 13.5 14.9 16.0 15.5 17.3 16.5

(b) θ = 18.6°C, Po = 819.7 kPa:

p/kPa 5.3 8.4 14.4 29.2 62.1 74.0 80.1 102.0

3
V/cm 9.2 9.8 10.3 11.3 12.9 13.1 13.4 14.1

(a) C* = 164, Vm = 13.1 cm3; (b) C* = 264, Vm = 12.5 cm3

25.7 The adsorption of solutes on solids from liquids often follows a Freundlich isotherm. Check the applicability of this isotherm to
the following data for the adsorption of acetic acid on charcoal at 25°C and find the values of the parameters b and n.

[acid]/(mol dm−3) 0.05 0.10 0.50 1.0 1.5

wa/g 0.04 0.06 0.12 0.16 0.19

wa is the mass adsorbed per unit mass of charcoal.

b = 2.4, n = 1/0.16

25.9‡ A. Akgerman and M. Zardkoohi (J. Chem. Eng. Data 41, 185 (1996)) examined the adsorption of phenol from aqueous solution
1/𝑛
on to fly ash at 20°C. They fitted their observations to a Freundlich isotherm of the form cads = 𝐾. 𝐶𝑠𝑜𝑙 , where cads is the concentration
of adsorbed phenol and csol is the concentration of aqueous phenol. Among the data reported are the following:

csol/(mg g−1) 8.26 15.65 25.43 31.74 40.00

−1
cads/(mg g ) 4.4 19.2 35.2 52.0 67.2
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Department of Physicochemical & Analytical Technologies

Determine the constants K and n. What further information would be necessary in order to express the data in terms of fractional
coverage, θ?
K = 0.138 mg g−1, n = 0.58

25.11‡ M.-G. Olivier and R. Jadot (J. Chem. Eng. Data 42, 230 (1997)) studied the adsorption of butane on silica gel. They report the
following amounts of absorption (in moles per kilogram of silica gel) at 303 K:

p/kPa 31.00 38.22 53.03 76.38 101.97 130.47 165.06 182.41 205.75 219.91
n/(mol kg −1) 1.00 1.17 1.54 2.04 2.49 2.90 3.22 3.30 3.35 3.36

Fit these data to a Langmuir isotherm, and determine the value of n that corresponds to complete coverage and the constant K.
n∞ = 5.78 mol kg−1, K = 7.02 Pa−1

25.12‡ The following data were obtained for the extent of adsorption, s, of acetone on charcoal from an aqueous solution of molar
concentration, c, at 18°C.
c/(mmol dm−3) 15.0 23.0 42.0 84.0 165 390 800
s/(mmol acetone/g charcoal) 0.60 0.75 1.05 1.50 2.15 3.50 5.10

Which isotherm fits this data best, Langmuir or Freundlich?

R (Langmuir) = 0.973, R(Freundlich) = 0.99994  Freundlich

25.31 The designers of a new industrial plant wanted to use a catalyst codenamed CR-1 in a step involving the fluorination of
butadiene. As a first step in the investigation they determined the form of the adsorption isotherm. The volume of butadiene adsorbed
per gram of CR-1 at 15°C varied with pressure as given below. Is the Langmuir isotherm suitable at this pressure?

p/kPa 13.3 26.7 40.0 53.3 66.7 80.0

3
V/cm 17.9 33.0 47.0 60.8 75.3 91.3

Investigate whether the BET isotherm gives a better description of the adsorption of butadiene on CR-1. At 15°C, Po (butadiene) =
200 kPa. Find Vm and C*.
BET isotherm is a much better representation of the data. Vm =75.4 cm3, C* = 3.98
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies

Appendix
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies
 Ho Chi Minh City University of Technology
Department of Physicochemical & Analytical Technologies