CALCULATIONS IN ADVANCED CHEMICAL ENGINEERING THERMODYNAMICS

Q1 Liquid-Vapor saturation pressure P Sat is often represented as a function of temperature

by an equation of the form:
P b
log10sat (torr) = a -
t(°C)+C

Here, parameters a, b, and c are substance-specific constants. Suppose it is required to

represent P Sat by the equivalent equation:
B
lnPsat (kpa) = A - (K)+C
T
Show how the parameters in the two equations are related.

Solution

Given:

P b
log10sat (torr) = a - … (1)
t(°C)+C

B
lnPsat (kpa) = A - … (2)
T (K)+C

1 torr = 0.1333kpa

P lnPsat (torr)
Log10sat (torr) =
2.303

P 1 Psat (kpa)
Log10sat (torr) = × ln
2.303 0.1333

P
log10sat(torr) = 0.4342 lnPsat (kpa) + 0.8749

Substituting in torr equation (1):

P b
log10sat(torr) = 0.4342 lnPsat (kpa) + 0.8749 = a −
t(°C)+C

b
0.4342lnPsat (kpa) = (a – 0.8749) -
t(°C)+C

b
0.4342lnPsat (kpa) = (a – 0.8749) -
T(K)−273.15+ C

2.303b
lnPsat (kpa) = 2.303(a – 0.8749) -
T(°C)−273.15+C

2.303b
lnPsat (kpa) = (2.303a – 2.0149) -
T(°C)−273.15+C

Comparing, we get,

A = 2.303a – 2.0149
B = 2.303b
C = c – 273.15

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Q2 The reading on a mercury manometer at 298.15 K (25°C) (open to the atmosphere at

one end) is 56.38 cm. The local acceleration of gravity is 9.832 m se2. Atmospheric pressure is
10 1.78 kPa. What is the absolute pressure in kPa being measured? The density
of mercury at 298.15 K (25°C) is 13.534 g cm-3

Solution

Given:

Psat = Pg + Patm … (3)

P = pgh … (4)

h = 56.38m @ 298.15k

g = 9.832m/s2

Patm = 101.78kpa = 101.78 × 103 Pa

Pabs =?

Density @ 298.15k = 13.534gcm-3

P = pgh

=13534 × 9.832 × 56.38

=7502277.317 Pa

Therefore, from equation (2):

Psat = Pg + Patm

= 750.2277(kpa) + 101.78(kpa)

= 7604.057kpa

Q3. The first accurate measurements of the properties of high-pressure gases were made by
E. H. Amagat in France between 1869 and 1893. Before developing the dead-weight gauge, he
worked in a mine shaft, and used a mercury manometer for measurements of
pressure to more than 400 bar. Estimate the height of manometer required.

Solution

P = pgh

Where,
P = Pressure of the gas
p = density of mercury = 13593kg/m3 (data from the internet)
h = Height of the manometer required

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Therefore,

P 4×107
h= = = 300.27m
𝑃𝑃g 13593×9.8

Q6 Pressures up to 3000 atm are measured with a dead-weight gauge. The piston diameter
is 0.17 (in). What is the approximate mass in (lb.) of the weights required?

Solution

Given:

P = 3000atm = 30397500 Pa
d = 0.17in = 0.004318m
M=?
𝑚𝑚𝑚𝑚 𝑃𝑃𝑃𝑃
From P = ;m= … (5)
𝐴𝐴 𝑔𝑔

Solving for area (A):

1 1
A = πd2 = (3.142) (0.004318)2 = 1.4646×10-5 m2
4 4

From equation (5):

30397500 ×1.4646 ×10−5

m= = 45.427kg ⇒ 100.12lb
9.8

Q7. A non-conducting container filled with 25 kg of water at 293.15 K (20°C) is fitted with
a stirrer, which is made to turn by gravity acting on a weight of mass 35 kg. The weight falls
slowly through a distance of 5 m in driving the stirrer. Assuming that all work done on the
weight is transferred to the water and that the local acceleration of gravity is 9.8 m sp2,
determine:
(a) The amount of work done on the water.
(6) The internal-energy change of the water.
(c) The final temperature of the water, for which Cp = 4.18 kJ kg-' 'C-'.
(d) The amount of heat that must be removed from the water to return it to its initial
temperature.
(e) The total energy change of the universe because of (1) the process of lowering the
weight, (2) the process of cooling the water back to its initial temperature, and (3)
both processes together.

Solution

(a) Assume all the work done on the weight is transferred to the water, so workdone on the
water is equal to workdone on the water is equal to workdone on the weight. Here, the
elevation of weight (35kg) to a 5m distance produces a change in its potential energy
(Ep).

W = Ep

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W = mg∆z
=35×9.8×5
= 1715kgm2/s2
... workdone on water, W is 1715kgm2/s2 = 1715J = 1.715kj

(b) From the first law of thermodynamics,

U = Q+ W … (6)
The container is made of non-conducting material and all the workdone on the weight is
transferred to the water so that no heat is transferred to the surroundings.
... Q = 0
Then,
∆U = 0 + 1.715Kj
∆U = 1.715Kj

(c) The specific heat capacity of water at constant pressure, Cp is 4.18kj/kg°C

The expression for the enthalpy is as follows:
H = U + PV
dH = dU + d(PV)
dH = dU + PdV + VdP … (7)

During the process, the pressure of the system is not changed

... dP = 0
dH = CpdT, then eqn (7) is as follows:
dH = dU + PdV
CpdT = dU + PdV … (8)
Multiply with mass of water on both sides of the above eqn:
... mCpdT = mdU … (9)
The expression for the final temperature of water is as follows:
Integrate eqn (4) from temperature T1 to T2 and internal energy from U1 to U2:

𝑇𝑇
2 2 𝑈𝑈
∫𝑇𝑇 𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚 = ∫𝑈𝑈 𝑚𝑚𝑚𝑚𝑚𝑚
1 1

Here, m and Cp are constants

𝑇𝑇 𝑈𝑈
𝑚𝑚𝑚𝑚𝑚𝑚 ∫𝑇𝑇 2 𝑑𝑑𝑑𝑑 = m∫𝑈𝑈 2 𝑑𝑑𝑑𝑑
1 1

Substitute ∆U for m (U2 – U1) in the above:

mCp (T2 – T1) = ∆U

∆𝑈𝑈
T2 – T1 =
𝑚𝑚𝑚𝑚𝑚𝑚

∆𝑈𝑈
T2 = T1 + … (10)
𝑚𝑚𝑚𝑚𝑚𝑚

Substitute 20c for T, 1.715kj for ∆U, 4.18kj/kg°C for Cp and 25kj for m in eqn (10)

1.715
T2 = 20 +
25 ×4.18

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T2 = 20 + 0.016
= 20.02°C

Therefore, the final temperature of the water, T2 is 20.02°C

(d) For the process of returning the water temperature to its initial temperature, the change
in internal energy is equal to the initial process internal energy change with opposite sign.
So,

∆U (Restoration) = - ∆U (Initial)
∆U (Restoration) = -1.715kj

The workdone in this process W = 0, the heat that must be removed from the water to
return it to its original state is as follows:

Q (Restoration) = ∆U (Restoration) + W (Restoration)

= -1.715kj + 0
= -1.715kj

(e) The total energy of the universe is always constant. Therefore, the change in total
internal energy of the universe is zero in all the cases.

Q8. An egg, initially at rest, is dropped onto a concrete surface and breaks. With the egg

treated as the system,

(a) What is the sign of W?
(b) What is the sign of ∆Ep?
(c) What is ∆EK?
(d) What is ∆Ut?
(e) What is the sign of Q?
In modeling this process, assume the passage of sufficient time for the broken egg to
return to its initial temperature.

Solution

(a) W is negative because workdone is on the system

(b) ∆Ep is negative because the system decreases in gravitational potential energy
(c) ∆EK is zero because it began at rest and ended at rest
(d) ∆U is zero because it returned to its initial temperature
(e) Q is negative because heat is released to the environment

Q9. An electric motor under steady load draws 9.7 amperes at 110 volts, delivering 0.93 kW
of mechanical energy. What is the rate of heat transfer from the motor, in kW?
Solution
Given:

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Current (I) = 9.7 Ampere

Voltage (V) = 110 volts
Mechanical Energy (E) = 0.93 KW
Power of motor = I × V
= 9.7 × 110 = 10.67W = 1.067 KW
Therefore, heat transfer from the motor = Power – Mechanical energy
= 1.067 – 0.93
= 0.137 KW

Q10. Comment on the feasibility of cooling your kitchen in the summer by opening the door
to the electrically powered refrigerator.

Solution
It is not feasible; the kitchen would get warmer. Energy coming to the refrigerator is used to
compress the refrigerant. The refrigerant, after being compressed must be condensed and the
heat of condensation is given up to the kitchen. The refrigerant after condensation is throttled
and becomes a two-phase mixture at low temperature and can now absorb heat inside the
refrigerator.

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