Chemical Engineering Thermodynamics (Odd Semester 2023-24)

Home work 7
(Due by 30th September 2023)

1. If in a mixture of C molecular species containing Ni molecules of ith kind with total number of
molecules being N, the ΔNi molecules of the ith kind is introduced. Obtain expressions for the
change in the mole fractions Δx for each species.

2. Obtain the analog of the Gibbs Duhem equation at (i) constant temperature and volume, and (ii)
constant entropy and volume.

3. From the following figure showing the variations of volume change upon mixing in methanol-
methyl formate (white dots) and ethanol-methyl formate (solid dots) at 298.15 K, compute the
partial molar volume of methyl formate at various compositions in the two mixtures at the same
temperature:

4. In an experiment, water is added in varying amounts to one mole of sulfuric acid at room
temperature and heat evolved is recorded. The folloing data is available:

Number 0.25 1.00 1.50 2.33 4.00 5.44 9.00 10.10 19.00 20.00
of
moles
of water
added
Heat 8242 28200 34980 44690 54440 58370 62800 64850 70710 71970
released
(J)
 Using the above data, compute the heat released when 100 g of pure sufuric acid is added to
100 g of water at room temperature.

5. The heat of mixing data for the n-octanol (species '1') and n-decane (species '2') liquid mixture
at atmospheric pressure is approximately fit by the following equation:
mix H =x 1 x2  A B  x1−x 2  , where A =-12974 + 51.505 T, and B = 8782.8 – 34.129 T, where
T is the temperature in K and mixing enthalpy is in J/mol.

(a) Compute the difference between the partial molar and pure component molar enthalpies of
equimolar mixture of n-octanol and n-decane at T = 300 K.

(b) Compute the difference between the partial molar and pure component heat capacities of the
two species in their equimlar mixtures at 300 K.

6. n an calorimetry experiment, fractions of pyridine (1) and acetic acid (2) are mixed and the
variation of the enthalpy change of mixing with the composition is obtained as below:

Mole 0.037 0.071 0.103 0.134 0.162 0.189 0.219 0.249 0.276 0.300 0.323 0.346 0.367 0.287 0.399
fractio 1 6 2 0 5 6 0 4 0 6 4 1 1 4 1
n (1)
−mix H1006. 1851. 2516. 3035. 3427. 3765. 4043. 4271. 4440. 4571. 4676. 4760. 4819. 4863. 4882.
(J/mol) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Mole 0.407 0.423 0.450 0.478 0.502 0.530 0.562 0.596 0.637 0.674 0.713 0.757 0.808 0.865 0.929
fractio 6 5 0 6 9 7 1 8 2 7 8 8 3 4 0
n (1)
−mix H 4880. 4857. 4855. 4833. 4765. 4669. 4496. 4253. 3950. 3547. 3160. 2702. 2152. 1524. 0806.
(J/mol) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Two streams containing pyridine and acetic acid at 25oC are mixed and fed to a heat exchanger.
Due to the heat of mixing effect, it is desired to reduce the temperature of the mixture to 25oC
using a stream of chilled ethylene glycol as indicated in the diagram. The heat capacity of the
ethylene glycol at these conditions is approximately 2.8 kJ/(kg.K). Compute the mass flow rate
of the ethylene glycol needed.