KKKR2383 Example Questions For Chapter I PDF

Example 1.
1
(a) By starting from the following equation,
⎡ ⎛ ∂P ⎞ ⎤
dU = CV dT + ⎢T ⎜ ⎟ − P ⎥ dV
⎣ ⎝ ∂T ⎠V ⎦
obtain expressions for the derivatives (∂U ∂T )V and (∂U ∂T )P , and show that they are not
equal.
(b) The constant pressure heat capacity, CP of liquid water at 25oC and 1 bar is 4.18 kJ/kg.K.
Estimate the heat capacity of liquid water at 25oC and 100 bar. Given:
⎛ ∂CP ⎞ ⎡ 2 ⎛ ∂α ⎞ ⎤
⎜ ⎟ = −T ⎢α V + V ⎜ ⎟ ⎥
⎝ ∂P ⎠T ⎣ ⎝ ∂T ⎠ P ⎦
⎛ ∂α ⎞ −6 −2
where V=1.003 cm3/g, α = 2.56 × 10 −4 K −1 and ⎜ ⎟ = 9.6 ×10 K . Assume that the
⎝ ∂T ⎠ P
⎛ ∂C ⎞
thermodynamic property ⎜ P ⎟ is reasonably constant with pressure change.
⎝ ∂P ⎠T
Example 1.2
(a) The following is the Clausius/Clayperon equation:
d ln P sat
ΔH lv = − R
d (1 T )
with, ΔH, ΔV and Psat are respective latent heat of vaporization, volume change and vapour
pressure during a phase change process. Based on the above Clausius/Clayperon equation, derive
the Clapeyron equation as follows:
dP sat ΔH lv
=
dT TΔV lv
State all the assumptions made during the derivation of the Clausius/Clayperon equation,
and also, state any condition that can apply this equation.
(b) The following data are the vapour pressure of carbon tetrachloride:
t (oC) 25 35 45 55
sat
P (mmHg) 113.8 174.4 258.9 373.6
Based on the data, plot a suitable diagram that can be used to estimate the latent heat of
vaporization for carbon tetrachloride.
Example 1.3
(a) The Clayperon equation is as follows:
dP sat ΔH lv
=
dT TΔV lv
with, ΔH, ΔV and Psat are respective latent heat of vaporization, volume change and vapour
pressure during a phase change process. Based on the above Clapeyron equation, derive the
Clausius/Clayperon equation in a linear form, Y=MX+C. State all the assumptions made during
the derivation of the Clausius/Clayperon equation, and also, state any condition that can apply
this equation.
(b) The temperature change for transition process of rhombic sulphur to monoclinic sulphur with
the pressure are as in the following table:
P (atm) 1 100 360 610 850
t (oC) 95.5 100 110 120 130
At 1 atm, the volume change for the process was measured as 13.8 cm3kg-1. Determine
the heat change for this process at 1 atm. Compare the obtained value with this value of 401.7 J/g
atom, obtained from the calorimetric analysis (Conversion unit: 1 g atom = 0.03206 kg).
Example 1.4
Vapor pressure of benzene is given by the following equation:
2788.51
ln P sat / kPa = 13.8858 − o
t/ C + 220.79
Estimate the entropy change for the vaporization process of benzene at 50oC by using:
(a) Clayperon equation, and
(b) Clausius/Clapeyron equation
for the approximation value of ΔVlv. Compare the results and give the conclusion.
Example 1.5
(a) Explain what is meant by equation of state, and give the types of cubic equations of state
with their respective applications.
(b) For a real gas, Van der Waals is as follows:
⎛ a ⎞
⎜ P + 2 ⎟(v − b ) = RT
⎝ v ⎠
with pressure P, absolute T, gas constant R, molar volume v and, a and b are constants for a
certain gas.
(i) Show at the critical point:
8a a 3
v c = 3 b; RTc = ; Pc = 2
; zc =
27b 27b 8
∂P ∂ 2P
(Tips: use the condition required at an inflexion point at P-v, = 0 and = 0)
∂v ∂v 2
(ii) By assuming Van der Waals equation is complied, determine the temperature of
9.203 kg oxygen gas that fills a cylinder of 40 dm3 at P=150 atm. The critical
conditions for oxygen are Pc=5036 kN/m2 dan Tc=154.4 K.
Example 1.6
5 moles of calcium carbide is combined with 10 mol of liquid water in a closed, rigid, high
pressure vessel of 750 cm3 capacity. Acetylene gas is produced by the reaction:
CaC2(s) + 2H2O(l) → C2H2(g) + Ca(OH)2(s)
Initial conditions are 25oC and 1 bar, and the reaction goes to completion. For a final temperature
of 125oC, determine:
(a) The final pressure, and
(b) the heat transferred.
At 125oC, the molar volume of Ca(OH)2 is 33.0 cm3mol-1. Ignore the effect of any gas present in
the vessel initially.
Example 1.7
Ethylene gas at 130oC and 150 bar expands in a steady-flow process to a final state at 0oC and 1
bar. Assume that the ethylene gas behave ideally at the final state. The following data are the
critical properties of ethylene:
Tc=282.3 K Pc=50.40 bar ω=0.087
(a) Develop steps in the form of a calculational path diagram in order to determine entropy and
enthalpy change for the whole process.
(b) Based on the calculational path diagram in part (a), determine the entropy and enthalpy
change for each step.
C Pig
Given, = 1.424 + 14.394 × 10 −3 T − 4.392 × 10 −6 T 2 with [T ] = Kelvin .
R
(c) What is value for the residual enthalpy, H2R and residual entropy, S2R at the final state?
(d) Determine the entropy and enthalpy change for the overall process.

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Example 1.

P (atm) 1 100 360 610 850

t (oC) 95.5 100 110 120 130

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