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ThermoII Exercise 1

Here are the steps to estimate VR, HR, and SR for carbon dioxide at 400 K and 200 bar using appropriate generalized correlations: 1) Use the Span-Wagner EOS to calculate the compressibility factor Z at 400 K and 200 bar. This will give the reduced volume VR. 2) Use the modified Twu equation to calculate the reduced enthalpy HR from the temperature and compressibility factor. 3) Use the modified Twu equation to calculate the reduced entropy SR from the temperature and compressibility factor. The Span-Wagner EOS and modified Twu equations are generalized correlations that can estimate thermodynamic properties for carbon dioxide over a wide range of conditions. Plugging the given

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Batuhan Kalyoncu
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409 views53 pages

ThermoII Exercise 1

Here are the steps to estimate VR, HR, and SR for carbon dioxide at 400 K and 200 bar using appropriate generalized correlations: 1) Use the Span-Wagner EOS to calculate the compressibility factor Z at 400 K and 200 bar. This will give the reduced volume VR. 2) Use the modified Twu equation to calculate the reduced enthalpy HR from the temperature and compressibility factor. 3) Use the modified Twu equation to calculate the reduced entropy SR from the temperature and compressibility factor. The Span-Wagner EOS and modified Twu equations are generalized correlations that can estimate thermodynamic properties for carbon dioxide over a wide range of conditions. Plugging the given

Uploaded by

Batuhan Kalyoncu
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Problem1:

How many phase rule variables must be specified to fix


the thermodynamic state of each of the following
systems?
(a) A sealed flask containing a liquid ethanol-water
mixture in equilibrium with its vapor.
(b) A sealed flask containing a liquid ethanol-water
mixture in equilibrium with its vapor and nitrogen.
(c) A sealed flask containing ethanol, toluene, and water
as two liquid phases plus vapor.
Problem 2:
A renowned laboratory reports quadruple-point coordinates
of 10.2 Mbar and 24.1°C for four-phase equilibrium of
allotropic solid forms of the exotic chemical β-miasmone.
Evaluate the claim.
Problem 3:
A system comprised of chloroform, 1,4-dioxane, and
ethanol exists as a two-phase vapor/liquid system at 50°
C and 55 kPa. After the addition of some pure ethanol,
the system can be returned to two-phase equilibrium at
the initial T and P. In what respect has the system
changed, and in what respect has it not changed?
Problem 2

Generally, volume expansivity β and isothermal


compressibility κ depend on T and P.
Prove that:
Problem 2
Express the volume expansivity and the isothermal compressibility
as functions of density ρ and its partial derivatives. For water at 50°
C and 1 bar, κ = 44.18×10-6 bar-1 . To what pressure must water be
compressed at 50°C to change its density by 1%? Assume that κ is
independent of P.
Problem 3

The Tait equation for liquids is written for an isotherm as:

where V is molar or specific volume, V0 is the hypothetical molar


or specific volume at zero pressure, and A and B are positive
constants. Find an expression for the isothermal
compressibility consistent with this equation.
Problem 7:
For one of the substances in Table 3.2, compute
the final pressure when the substance is heated
from 15°C and 1 bar to 25°C at constant volume.
Problem 8:
A substance for which κ is a constant undergoes an
isothermal, mechanically reversible process from initial state
(P1, V1) to final state (P2, V2), where V is molar volume.
(a) Starting with the definition of κ, show that the path of the
process is described by:

(b) Determine an exact expression which gives the


isothermal work done on 1 mol of this constant-κ substance.
Problem 9: One mole of an ideal gas with CP = (7/2)R and CV =
(5/2)R expands from P1 = 8 bar and T1= 600 K to P2= 1 bar by
each of the following paths:
(a) Constant volume;
(b) Constant temperature;
(c) Adiabatically.
Assuming mechanical reversibility, calculate W, Q, ΔU, and ΔH for
each process. Sketch each path on a single PV diagram.
Problem 10.
An ideal gas, initially at 30°C and 100 kPa, undergoes the following cyclic processes in a closed system:
(a) In mechanically reversible processes, it is first compressed adiabatically to 500 kPa, then cooled at a constant
pressure of 500 kPa to 30°C, and finally expanded isothermally to its original state.
(b) The cycle traverses exactly the same changes of state, but each step is irreversible with an efficiency of 80%
compared with the corresponding mechanically reversible process. Note: The initial step can no longer be
adiabatic.
Calculate Q, W, ΔU, and ΔH for each step of the process and for the cycle. Take CP = (7/2)R and CV = (5/2)R.
Problem11:
One cubic meter of an ideal gas at 600 K and 1000 kPa
expands to five times its initial volume as follows:
(a) By a mechanically reversible, isothermal process.
(b) By a mechanically reversible, adiabatic process.
(c) By an adiabatic, irreversible process in which expansion is
against a restraining pressure of 100 kPa.
For each case calculate the final temperature, pressure, and
the work done by the gas. Take CP = 21 J・mol-1K-1
Problem :

The vapor-phase molar volume of a particular compound is


reported as 23,000 cm3・mol-1 at 300 K and 1 bar. No other data
are available. Without assuming ideal-gas behavior, determine a
reasonable estimate of the molar volume of the vapor at 300 K
and 5 bar.
Problem
Estimate the following:
(a) The volume occupied by 18 kg of ethylene at 55°C and 35 bar.
(b) The mass of ethylene contained in a 0.25 m3 cylinder at 50°C and 115 bar.
Problem:To a good approximation, what is the molar
volume of ethanol vapor at 480°C and 6000 kPa? How
does this result compare with the ideal-gas value?
Problem: To what pressure does one fill a 0.15 m3
vessel at 25°C in order to store 40 kg of ethylene
in it?
Example: Comparison of Methods

Calculate the molar volume of ethylene at 40°C, 90 bar, using the


(a) ideal-gas law,
(b) the truncated virial equation, and
(c) the Pitzer correlation with the Lee-Kesler values for Z0, Z1

Solution The critical parameters of ethylene are Pc= 50.41 bar, Tc= 282.34 K, ω = 0.087.

The reduced coordinates are (a) Ideal-gas law: The ideal-gas molar volume is

(b) Virial equation: We first calculate the second virial coefficient using following eqs.
The compressibility factor is calculated form the truncated virial equation

and the molar volume is


Lee-Kesler correlation The values of Z0, Z1, are
Problem 4: (6.92) Prove that

For an ideal gas with constant heat capacities, use this result to derive P(Vig) γ  = const
Problem 5: (6.93) The derivative (∂U/∂V)T is sometimes called the internal pressure and the
product T(∂P/∂T )V the thermal pressure. Find equations for their evaluation for:
(a) An ideal gas;
(b) A van der Waals fluid;
(c) A Redlich/Kwong fluid.
Problem 6: Estimate the molar volume, enthalpy, and entropy for n-butane as a saturated vapor
and as a saturated liquid at 370 K. The enthalpy and entropy are set equal to zero for the ideal-gas
state at 101.33 kPa and 273.15 K. The vapor pressure of n-butane at 370 K is 1435 kPa.
Problem 7: Estimate VR H R, and S R for one of the following by appropriate generalized
correlations:
(a) Carbon dioxide at 400 K and 200 bar.

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