LT # 1 VOLUMETRIC PROPERTIES Group No.1 Name Borres, Kristian Jude I. Deduyo Roel Gimena, Mary Kris L.

Rivera, Redden Rose C. Signature

Problem 1: Derive the Van der Waals Equation of State in terms of its parameters, a and b. Also, derive the equation for these parameters and use them to approximate the molar volume of water vapor at 400oC and 3500 kPa with an experimental molar volume of 1545.5m3.
Given: Required: T = 400oC = 673 K P = 3500 kPa = 35 bar

Derive VdW parameters, a and b Molar volume, Vm

From Table 3.1: Parameter Assignments for VdW EOS: of Introduction to Chemical Engineering Thermodynamics (Smith and Van Ness) (t)

Solution:

VdW EOS

1/8

27/64

Vapor and vapor like roots of the generic cubic equation of state: V = RT + b a (T) V-b P P (V+b) (V+b) V = RT + b a (T) V-b P P V2 Solving for parameters a and b: = bP RT = Pr Tr for Vdw EOS: = 1 Pr = 1 8 Tr 8 (3.50) (3.53) q = a(T) bRT q = (Tr) Tr (3.51) (3.54) ; and are zero for VdW EOS

P/Pc T/Tc

-- eqn (1)

q=

(27/64) (1) = 27 = 27 Tc (1/8) Tr 8Tr 8T

-- eqn (2)

Equating equations (1) and (3.50): 1 P/Pc = b P 8 T/Tc RT b = 1 RTc 8 Pc

Equating equations (2) and (3.51) 27 Tc 8T = a(T) bRT ; a(T) =27bRTc =27 1RTc RTc 8 8 8 Pc

a = 27 R2 Tc2 64 Pc

We can readily solve Vm using: V = RT + b a V-b P P V2 where: b = 1 RTc 8 Pc

a = 27 R2 Tc2 64 Pc

Ans.

From Appendix B.1 of Introduction to Chemical Engineering Thermodynamics (Smith and Van Ness):

Water:

Pc = 220.55 bar =

Tc = 647.10 K

a = 27 (83.14)2 (647.1)2 64 220.55 b = 1 (83.14) (647.1) 8 220.55

5, 536, 554.356

= 30.492

V = (83.14)(673) + 30.492 5,536,554.356 35 35

V 30.492 V2

By trial and error: assume Vm = VM, IDEAL = RT = (83.14)(673) = 1598.7 cm3/mol P 35 Vassumed Vcomputed 1598.7 1532.1 1532.1 1528.0 1528.0 1527.7 1527.7 1527.7 ; Vm = 1527.7 cm3/mol Ans. %Error = 1.15%

Problem 2 Approximate the molar volume of formaldehyde at 1050 K and 75 bar using virial equation method. Compare the result with ideal-gas value.
Given: T=1050 K P=75 bar Required: molar volume of formaldehyde using virial equation method Assumptions: Solution: The Virial Equation Method is given by the following: There are no ideal gas assumptions

From Appendix B.1 of Introduction to Chemical Engineering Thermodynamics (Smith and Van Ness):

From For formaldehyde:

TC=408 K

PC=65.9 bar

=0.282

Ans.

% Error=1.25 %

Problem 3: A fixed amount of water vapor, initially 176.4 bar, 309.74 0C, is cooled at constant volume until its temperature reaches 2000C. Using the compressibility factor by Pitzer correlations, determine: a.) The specific volume of the water vapour in cm3/g at the initial state. b.) The pressure in kPa at at the final state.
Given: Required: Solution: T1 = 309.74 oC T2 =200 oC P = 176.4 bar

Specific volume of water at initial state Pressure at the final state

a. Z=Z0 + Z1 Known: Water vapor is cooled at CONSTANT VOLUME from 176.4 bar. 309.74 0C to 200 0C Assumptions: 1. Water is a closed system 2. The initial and final state are equilibrium Using Table B.1 (Van Ness), for water: Tc=647.1K, Pc=220.55 bar and =0.345 Tr=(309.74 + 273.15)K/647.1K = 0.90 Pr=176.4 bar/220.55 bar = 0.80

Using table E.1 and table E.2: Lee/Kesler Table (Van Ness) , at T r=0.90 and Pr=0.80, Z0=0.1321, Z1=0.0503. Therefore, Z=0.1321 + (0.345)(-0.0503) = 0.115 PV/(RT) = 0.115 the value for R is 83.14 cm3-bar/(mole-K) V=31.59 cm3/mole x (1 mole/18 g) = 1.755 cm3/g

Ans.

b. Using Pitzers correlations for second virial coefficient: Z=1 + B(Pr/Tr) = P2V/(RT2) Take note that Pr=P2/Pc Manipulating the equation by having only P2 to the left side of the equation: P2 = 1/[(V/(RT2) - B/(PcTr)] (Working Equation) Since B=B0 + B1 where the formulas of B0 and B1 are from equations 3.65 and 3.66 (Van Ness): B0=0.083 - 0.422/(0.731.6)=-0.615 B=-0.79 Substituting all the values to the working equation, P2=175.10 bar x 101.325 kpa/1 bar P2=17742.0075 kPa B1 = 0.139-0.172/(0.734.2) = -0.506

Ans.

-Michael Moran and Howard Shapiro. Fundamentals of Engineering Thermodynamics