TECHNOLOGICAL INSTITUTE OF TH E C (diamond) → C (graphite) The molar enthalpy change (heat

PHILIPPINES per one mole of this transition is ∆H mtr = -1.90 kJ mol-1 at 25

o
COMPETENCY EXAM IN PHYSICAL CHEMISTRY C and normal pressure. In the temperature range between 25
NAME __________________DATE__February 3, 2014 ; oC and 250 oC, the molar heat capacities (C mp) of diamond
Direction: Encircle the letter that corresponds to the and graphite are 6.06 and 8.64 J K-1 mol-1, respectively.
correct answer and provide the solution to the problem Calculate the molar enthalpy of the considered phase
solving. transition at 250 oC
a) -1.12 kJ mol-1 b) -1.22 kJ mol-1
1. With the help of chemical tables calculate the volume (V) c) -1.32 kJ mol-1 d) -1.42 kJ mol-1
of that methane sample at temperature 25oC and pressure
101.3 kPa, providing the ideal gas 10) Gibbs phase rule. What is the necessary number of
behavior of methane. intensive variables (intensive state quantities) defining the
a) 2.851×10-4 m3 b) 3.051×10-4 m3 state of the following systems (in equilibrium): Hydrogen gas
c) 3.541×10-4 m3 d) NOTG pressurized in a cylinder.
a) 1 b) 2 c) 3 d) NOTG
2.) Consider preparing the solution (liquid mixture) composed
of two liquids, acetone (1) and methanol 11). Absorbance A = 0.875 of the aqueous solution of K2PtCl6,
(2); M1 = 58.8 g mol-1, M2 = 32.04 g mol-1. If we mix with concentration c = 2.5×10-4 mol
together 5 g of each of the liquids, what are the molar fractions dm-3, was measured by a spectrophotometer in a cell with the
(x1, x2) of these components in the optical path length b = 2.0 cm at the wavelength
prepared mixture? l = 264 nm. Calculate: Absorbance of the solution of K2PtCl6
a) x1 = 0.4554 b) x1 = 0.6446 with concentration c = 4.0×10-5 mol dm-3, in the cell with b =
c) x1 = 0.3554 d) x1 = 0.5446 5.0 cm, at the same wavelength.
a.) A =0.150 b) A =0.250
Linked problems 3-4 c) A =0.280 d) A =0.350
3) Concentrated hydrochloric acid is aqueous solution of about
36% HCl (w/w) and the density of this solution is 1180 kg m-3. Linked problems 12 - 15
The relative molecular weights are: HCl 36.46 and H2O 18.02. The pressure of the saturated vapor of benzene (vapor in
Using the concentrated solution ,cm3 of concentrated acid, equilibrium with liquid) is 101.32 kPa at
how do you prepare 1 dm3 (1 l) of 0.05 M aqueous solution of 80oC and 4.81 kPa at 5.5oC, respectively. The latter pressure
HCl. and temperature correspond to the triple
a)42.92 b)8.58 c) 4.29 d)NOTG point of benzene.Calculate:
4) Calculate the approximate pH of the prepared diluted 12) the approximate molar heat of vaporization ∆H mv of
solution. benzene
a)0.3 b)1.0 c) 1.3 d) NOTG a) 23.47 kJ mol-1 b) 33.47 kJ mol-1
c) 39.47 kJ mol-1 d) 43.77 kJ mol-1
5) Radionuclide 11C6 (radioactive carbon isotope) is used in 13) Calculate the boiling point under a reduced
the so called positron emission tomography (PET) but due to pressure 10 kPa.
the electron-positron annihilation the emitted radiation a) 10 oC b) 20 oC c) 30oC d) NOTG
(gamma rays) consists of photons with energy e = 511 keV. 14) Under what pressure benzene boils at 10oC?
What is its frequency (n)? a) 6.05 kPa b) 4.81 kPa
a)1.24×1020 Hz b) 2.24×1020 Hz c) 3.87 kPa d) 2.98 kPa
c) 3.44×10 Hz d)4.48×1020 Hz
20
15) What is the saturated vapor pressure over solid benzene in
the triple point (5.5oC)?
6) Molar refraction Rm is an additive property, sometimes it is a) 6.05 kPa b) 4.81 kPa
regarded as a sum of the increments c) 3.87 kPa d) 2.98 kPa
of chemical bonds, e.g.: C-C 1.21 cm3 mol-1, C=C 4.15 cm3
mol-1, C-H 1.7 cm3 mol-1, etc. Liquid hydrocarbon C6H12 has Cryoscopic constant of benzene is Kc = 5.10 K kg mol-1. The
density = 778.4 kg m-3 and its refractivity index n = 1.4260. solidifying temperature of the solution composed of 150 mg of
Using the molar refraction, decide if it is hexene or the investigated compound in 20 g of benzene was measured
cyclohexane. and it was by 0.444 lower than the solidifying temperature of
a) Rm = 27.70 cm3 mol-1, hexene pure benzene.
b) Rm = 29.39 cm3 mol-1, hexene 16) Calculate the molar mass of the investigated compound
c) Rm = 27.66 cm3 mol-1,cyclohexane a) 0.0861 kg/ mol b) 0.0982 kg/mol
d) Rm = 29.39 cm3 mol-1,cyclohexane c) 0.1053 kg/mol d) 0.1561 kg/mol

6) The respective half-lifes t1/2 of the reaction in dilute and

acidified aqueous solutions were measured by polarimetry at Linked Problems 17-19
various temperatures, with the initial concentration of For water, ebulioscopic constant is Ke = 0.52 K dm3 mol-1 and
saccharose 0.2 mol dm-3, and it was found: 50 oC, t 1/2 = 23.0 cryoscopic constant Kc = 1.86 K dm3 mol-1, respectively. The
s; 25°C, t1/2 = 673 s; 10 oC, t1/2 = 111.7 min. Calculate: rate 0.710 g sample of Na2SO4 (Mr = 142.0) was dissolved in
constants (k) of the reaction at 50 oC water, so that 250 cm3 of
a) k = 1.03×10-3 s-1 b) 50oC: k = 0.0301 s-1 the aqueous solution was prepared. Disregarding the osmotic
-3 -1
c) k =0.103×10 s d) k = 3.01 x 10-3 s-1 coefficient, Calculate 15 - 18:
17) Boiling temperature of the prepared solution at normal
7) Calculate time of 90% inversion of saccharose at 25°C, pressure.
a)76.5 s b) 37.2 min c) 6.2 h d) 10.8 h a) 100.03°C b) 100.08°C c) 100.12°C d) 100.25°C
8) Using the reaction constants at 10 oC and 50 oC, calculate 18) Freezing temperature of the solution.
the activation energy (E) of the reaction. a) -0.012 °C b) -0.12 °C c) -0.112 °C d) -0.212 °C
a) E = 108 kJ mol-1 b) 210 kJ mol-1 19) Osmotic pressure of the solution (p) at 0°C
-1
c) E = 368 kJ mol d) E = 452 kJ mol-1 a) 136 kPa b) 149 kPa c) 186 kPa d) 198 kPa

9) An example of the phase transition is the change of the 20) The hypotonic aqueous solutions used for injections and
crystalline modification of carbon: eye drops have to be isotonized by the addition of a suitable
excipient substance into the solution. Using the cryoscopic
constant of water from previous problem
calculate the amount (mass) of the excipient, necessary for the
isotonization of the 200 cm3 of the solution of vitamine B1,
conc. 20 mg in 1 cm3 (thiaminium dichloride, B2+(Cl-)2, Mr =
337.3), excipient galactose (Mr = 180.2).
a) 2.45 g b) 3.04 g c) 3.67 g d) NOTG
21)The solubility of iodine in CCl4 is 18.8 g dm-3 and in water
it is only 0.22 g dm-3 (20°C). How much % of iodine is
extracted into CCl4, if this aqueous solution is shaken
(extracted) two times with 25 cm3 of CCl4 in each run
a) 89.5% b) 94.6% c) 96.4% d) 99.3%
Linked problems 21 - 22
Ammonium cation NH+4 dissociate in diluted aqueous solution
according to the scheme:
NH+4 + H2O → NH3 + H3O+
At 25oC ammonium cation has pKA = 9.245 and its standard
dissociation enthalpy ∆𝐻𝑟𝑜 = 52.01 kJ mol-1.
21) Calculate pKA of the ammonium cation at 70 oC.
a) 4.45 b) 5.56 c) 6.24 d) 8.05
22) Calculate ∆𝐺𝑟𝑜 and ∆𝑆𝑟𝑜 of dissociation at 25oC.
a) ∆𝐺𝑟𝑜 = 22.77 kJ mol-1, ∆𝑆𝑟𝑜 = -1.55 J K-1 mol-1
a) log ± = -0.005, pH = 4.005
b) log ± = -0.016, pH = 3.016
c) log ± = -0.051, pH = 2.051 d) NOTG
30)The described electrochemical cell (concentration cell) was
set up: Cu|CuSO4 (c1) // CuSO4 (c2)|Cu
Determine which electrode is the positive terminal (+) of the
cell and calculate the cell potential E (electromotive force,
EMF) for the given concentrations of the electrolyte CuSO4 in
the cell (25oC): c1 = 0.01 mol dm-3, c2 = 1×10-4 mol dm-3
a) E = -0.0592 V, left hand side electrode (+)
b) E = 0.0592 V, right hand side electrode (+)
c) E = 0.0592 V, left hand side electrode (+)
d) E =- 0.0592 V, right hand side electrode (+)
Linked Problems 31-32
The reaction scheme of the elimination of iodine from organic
molecule is RI + HI → RH + I2 where R is an aliphatic
radical. The reaction is of the 2nd order, the rate constant is k
= 1.9×10-11 mol-1 dm3 s-1 at 25 oC and the activation energy of
the reaction is E = 106 kJ mol-1.31) Calculate the rate constant
and 32) how much the reaction is accelerated, if temperature is
raised from 25oC to 35 oC
31 a) k = 7.6×10- 11 mol-1 dm3 s-1 b) k = 2.8×10 mol-1 dm3 s-1
-10

b) ∆𝐺𝑟𝑜 = 52.77 kJ mol-1, ∆𝑆𝑟𝑜 = -2.55 J K-1 mol-1 c) k = 8.8×10-7mol-1 dm3 s-1 d) k = 6.4×10-10 mol-1 dm3 s-1
c) ∆𝐺𝑟𝑜 = 62.77 kJ mol-1, ∆𝑆𝑟𝑜 = -3.55 J K-1 mol-1 32) a) 15 times b) 4 times
d) ∆𝐺𝑟𝑜 = 52.77 kJ mol-1, ∆𝑆𝑟𝑜 = 2.55 J K-1 mol-1 c) 46000 times d)NOTG

Linked Problems 23-25 Linked Problems 33 -

The respective limiting ionic conductivities (at very large Acetic acid (CH3COOH, abbrev. HA) is a very common weak
dilution) of hydrogen ion (H+) and anion acid with pKA = 4.75 (at 25oC and low ionic strength). 33)
of butyric acid (A-) are λo(H+) = 34.98 mS m2 mol-1 and Calculate pH of the diluted solution of acetic acid with
λo(A-) = 3.26 mS m2 mol-1 (25°C). concentration c = 0.05 mol dm-3.
23) Calculate the limiting molar conductivity λo(HA) of a)3.02 b) 3.75 c) 4.02 d) 4.75
butyric acid (HA, weak electrolyte). Acetate buffer solution may be also prepared by the partial
a) o(HA) = 8.44 mS m2 mol-1 neutralization of HA with NaOH: 20 cm3 of the solution of
b) o(HA) = 21.21 mS m2 mol-1 NaOH, 0.1 mol dm-3 were mixed with 50 cm3 of the solution
c) o(HA) = 30.56 mS m2 mol-1 of HA with the same concentration, and water added up to 100
d) o(HA) = 38.24 mS m2 mol-1 cm3.34) Calculate the equilibrium concentration of [A-] and
24) Specific conductivities (ĸ) of two solutions of butyric acid 35) pH of the final buffer solution.
with mutually different concentrations were measured, for the 34) a) 0.03 mol dm-3 b) 0.02 mol dm-3
-3
first solution it was k = 4.436 mS m-1 at c = 0.001 mol dm-3 c) 0.018 mol dm d) 0.015 mol dm-3
and for the second one it was k = 14.31 mS m-1 at c = 0.01 mol 35) a) 4.32 b) 4.57 c) 5.12 d) 5.48
dm-3. Calculate the molar conductivity λ (HA) and the degree
of dissociation a of butyric acid in the 1st and
a)(HA) = 4.436 mS m2 mol-1, = 0.116;
b) (HA) = 5.46 mS m2 mol-1, = 0.06;
c) (HA) = 6.367 mS m2 mol-1, = 0.11;
d) (HA) = 8.977 mS m2 mol-1, = 0.16;
25) Calculate pH of butyric acid.
a) 3.93 b) 3.43 c) 5.46 d) 4.65
26) Calculate the pKA of butyric acid from the data for the two
solutions.
a) 4.82 b) 4.84. c) 6.56 d) 3.43

Linked problems 27 - 28
The general formula for ionic strength I (mol dm-3) of the
strong electrolyte solution is I = ½Σcizi2, where ci and zi are
the respective concentrations and charge numbers of all ions in
the solution. 27) Calculate the ionic strength of the solutions
of the electrolytes K4[Fe(CN)6] at concentration c = 0.01
mol/L.
a) 0.03 mol/L b) 0.04 mole/L
c) 0.06 mole/L d) NOTG
28) Three salts are dissolved in one solution: Mg(NO3)2 0.003,
MgSO4 0.005, K2SO4 0.007 mol dm-3. Calculate the ionic
strength of the solution.
a) 0.04 mol/L b) 0.05 mole/L
c) 0.06 mol/L d) 0.07 mol/L

29) Consider solutions of hydrochloric acid (HCl, strong acid)

with concentration of 0.01 mol dm . calculate the respective
-3

log ± of HCl and pH values of the solutions with regard to the

mean activities of HCl.