IV.

THERMODYNAMIC PROPERTIES OF FLUIDS

Initial purpose in this chapter is to develop from the first and second laws the
fundamental property relations which underlie the mathematical structure of
thermodynamics. From these, we derive equations which allow calculation of enthalpy
and entropy values from PVT and heat-capacity data. We then discuss the diagrams
and tables by which property values are presented for convenient use. Finally, we
develop generalized correlations which provide estimates of property values in the
absence of complete experimental information.

Property Relations for Homogeneous Phases

The first law for a closed system of n moles is:

For the special case of a reversible process,

Equations from previous chapters are here written:

Together these three equations give:

where U, S, and V are molar values of the internal energy, entropy, and volume.
This equation, combining the first and second laws, is derived for the special case of a
reversible process.

Immediate application of these equations is to one mole (or to a unit mass) of a

homogeneous fluid of constant composition. For this case, they simplify to:

1
 These fundamental property relations are general equations for a homogeneous
fluid of constant composition.

Maxwell's equations

Enthalpy and Entropy as Functions of T and P:

Consider first the temperature derivatives. The equation below defines the heat
capacity at constant pressure:

Combination of this equation gives:

The pressure derivative of the entropy results to the equation:

2
The corresponding derivative for the enthalpy is found to be:

The equation then becomes:

The functional relations chosen here for H and S are:

whence

3
The partial derivatives in these two equations are given by:

These are general equations relating the properties of homogeneous fluids

of constant composition to temperature and pressure.

Internal Energy as a Function of P

The pressure dependence of the internal energy is obtained by differentiation

of the equation, U=H-PV:

The Ideal-Gas State:

The coefficients of dT and dP are evaluated from heat-capacity and PVT data.
The ideal-gas state provides an example of PVT behavior:

The equation then reduces to:

where superscript "ig" denotes an ideal-gas value. These are merely restatements of
equations for ideal gases.

4
Alternative Forms for Liquids
Alternative form Equations result when ( V/ T)p is replaced by βV:

Also, if, in addition ( V/ P)T is replaced by –kV

These equations, incorporating β and k, although general, are usually

applied only to liquids. However, for liquids not near the critical point, the volume
itself is small, as are β and K. Thus at most conditions pressure has little effect on
the properties of liquids.
When (V/ T)p is replaced in favor of the volume expansivity, they become:

Since β and k are weak functions of pressure for liquids, they are usually
assumed constant at appropriate average values for integration.

The Gibbs Energy as a Generating Function

The fundamental property relations for homogeneous fluids of constant
composition given show that each of the thermodynamic properties U, H, A, and G
is functionally related to a special pair of variables. In particular,
dG= VdP-SdT

The Gibbs energy when given as a function of T and P therefore serves as a generating
function for the other thermodynamic properties, and implicitly represents complete
property information.

Residual Properties

Residual Gibb`s Energy: 5

Residual Volume
 Fundamental property relation for residual properties

Residual Entropy

General expressions for Hig and Sig

V. TWO-PHASE SYSTEM S
The curves shown in Fig. 1 represents phase
boundaries for a pure substance. A phase transition
at constant temperature and pressure occurs
whenever one of these curves is crossed, and as a
result the molar or specific values of the extensive
thermodynamic properties change abruptly. Thus,
the molar or specific volume of a saturated liquid
is very different from the molar or specific volume
of saturated vapor at the same T and P. This is true
as well for internal energy, enthalpy, and entropy. Figure 1. PT diagram for a pure substance
The exception is the molar specific Gibbs energy,
which for a pure species does not change during a phase transition such as melting,
vaporization, or sublimation.
For two phases α and β of a pure species coexisting at equilibrium,
Gα = Gβ (1)
Where Gα and Gβ – molar Gibbs energies of the individual phases
For two phases coexist in equilibrium when the temperature is changed,
dGα = dGβ (2)
VαdPsat – Sα dT = Vβ dPsat – Sβ dT (3)

dPsat Sβ – Sα ∆Sαβ (4)

= β α= αβ
dT V –V ∆V
The entropy change ∆S and the volume change ∆Vαβ occur when a unit amount
αβ

of pure chemical species is transferred from phase α to phase β at the equilibrium pressure
and temperature.
6
At equilibrium pressure and temperature upon integration of equation,
dH = TdS – VdP (5)
leads to latent heat of phase transition: ∆Hαβ = T∆Sαβ (6)
Also equivalent to: ∆Sαβ = ∆Hαβ /T (7)
Then, dPsat ∆Hαβ
=
dT T∆Vαβ (8)
which is the Clapeyron equation,
For the particularly important case of phase transition from liquid l and v,

dPsat ∆Hlv
=
dT T∆Vlv (9)

Example 1: For vaporization at low pressures, one may introduce reasonable approximations
by assuming that the vapor phase is an ideal gas and that the molar volume of the liquid is
negligible compared with the molar volume of the vapor. How do these assumptions alter the
Clapeyron equation?

Solution: ∆Vlv = Vv = RT/Psat

dPsat ∆Hlv
=
dT T∆Vlv

dPsat ∆Hlv
=
dT RT2/Psat

dPsat/Psat ∆Hlv
=
dT/T2 R

∆Hlv = -R d ln Psat
d(1/T) (10)

Clausius-Clapeyron Equation

 Relates the latent heat of vaporization directly to the vapor-pressure curve.

 ∆Hlv is almost constant, virtually independent of T.
 Not valid, ∆Hlv decreases monotonically with increasing temperature from the triple
point to the critical point, where it becomes zero.
 The equation is applicable only at low pressures.

Temperature Dependence of the Vapor Pressure of Liquids

The Clapeyron equation is an exact thermodynamic relation, providing a vital
connection between the properties of different phases. A plot of ln Psat vs. 1/T generally yields
a line that is nearly straight:
ln Psat = A – B/T (11)
where A and B are constants for a given species.
7
Another equation which is very useful is the Antoine’s equation.
B
Antoine’s equation: ln Psat = A − T+C (12)
 A principal advantage of this equation is that values off the constants A, B, and C
are readily available for a large number of species.

For accurate representation of vapor-pressure data over a wide temperature range requires an
equation of greater complexity which is Wagner’s equation:
Aτ + Bτ1.5 + Cτ3 + Dτ6
ln Psat = (13)
1–τ

τ = 1 – Tr
Other equation include:
Riedel’s Equation:
∆Hlv 1.092 (ln Pc – 1.013)
=
R Tn 0.930 – Trn (14)

Where: Tn = normal boiling point Pc = critical pressure

∆Hlv = latent heat of vaporization Trn = residual temperature at Tn

Two Phase Liquid/Vapor Systems

When a system consists a saturated-liquid and saturated vapor phases coexisting in
equilibrium, the total value of any extensive property of the two-phase system is the sum of
the total properties of the phases. Written for this relation:
M = (1 – xv) Ml + xv Mv= Ml + xv ∆Mlv (15)

where xl and xv, fractions of the total systems that are liquid and vapor called quality
M represents thermodynamic property (V, U, H, S, etc.)

VI. THERMODYNAMIC DIAGRAMS AND TABLES

A thermodynamic diagram is a graph showing for a particular substance a set of
properties. The most common diagrams are: TS, PH (usually ln P vs. H) and HS (called a
Mollier diagram). Thermodynamic diagrams usually show a net of five different lines:

 Isobars - lines of constant pressure

 Isotherms – lines of constant temperature
 Dry adiabats – lines of constant potential temperature representing the temperature of
a rising parcel of dry air
 Saturated adibats or pseudoadiabats – lines representing the temperature of a rising
parcel saturated with water vapour
 Mixing ratio – lines representing the dew point of a rising parcel

8
 Figure 2. PH diagram
Figure 3. TS diagram

Figure 3. properties
In many instances thermodynamic Mollier diagram
are tabulated. This has the advantage
that data can be represented more precisely than in diagrams, but the need for interpolation
is introduced. The steam tables are the most thorough compilation of properties for any
single material. However, tables are available for a number of other substances.

Example 2: Superheated steam originally at P1 and T1 expands through a nozzle to an

exhaust pressure P2. Assuming the process is reversible and adiabatic, determine the
downstream state of the steam and ∆H for the following conditions:
a. P1 = 1,000 kPa, t1 = 2500C, and P2 = 200kPa
b. P1 = 150 psia, t1 = 5000F, and P2 = 50 psia
Solution:
From the steam table,
At P1 =1000 kPa, T1 = 250°C, H1 = 2942.9 kJ/kg, S1 = 6.9252 kJ/kg.K
At P2 = 200 kPa, S2 = S1 = 6.9252 kJ/kg
Sl2 = 1.530 kJ/kg.K
Sv2 = 7.1268 kJ/kg.K

S2 = (1 – xv2) Sl2 + xv2 Sv2

6.9252 = 1.530 (1 – xv2) + 7.1268 xv2
xv2 = 0.9640

H2 = (1 – xv2) Hl2 + xv2 Hv2

H2 = (1 – 0.9640)(504.7) + (0.9640)(2706.3)

H2 = 2627.0 kJ/kg
 ∆H = H2 - H1
∆H = 2627.0 – 2942.9

∆H = -315.9 kJ/kg

VII. GENERALIZED PROPERTY CORRELATIONS FOR GASES

Compressibility factor, usually defined as Z = pV/RT, is unity for an ideal gas. In
most engineering work, the compressibility factor is used as a correction factor to ideal
behavior. Thus, Vreal = Z · Videal is used to calculate the actual volume, Vreal, as the product
of the compressibility factor and the ideal gas volume, all at the same pressure and
temperature. Z is most commonly found from a generalized compressibility factor chart as
a function of the reduced pressure, and the reduced temperature, where Pr and Tr are the
reduced variables and the subscript 'c' refers to the critical point.

Reduced Parameters
𝑇
𝑇𝑟 =
𝑇𝑐
𝑃
𝑃𝑟 =
𝑃𝑐
𝑉
𝑉𝑟 =
𝑉𝑐
Pitzer Correlations

𝑍 = 𝑍 ° + 𝜔𝑍1
Perry’s HB Eq. 2-63

The values for Z ⁰ and Z1 for gases are listed in the Perry’s HB Table 2-351 and 2-352,
respectively.

The Lee-Kesler correlation provides reliable results for gases which are nonpolar or only
slightly polar. When applied to highly polar gases, large errors can be expected.

Of the two kinds of data needed for evaluation of thermodynamic properties, heat
capacities and PVT data, the latter are most frequently missing. Fortunately, the
generalized methods developed for the compressibility factor are also applicable to residual
properties.

𝑃 = 𝑃𝑐 𝑃𝑟

𝑑𝑃 = 𝑃𝑐 𝑑𝑃𝑟
 𝑇 = 𝑇𝑐 𝑇𝑟

𝑑𝑇 = 𝑃𝑐 𝑑𝑇𝑟
The resulting equations are
𝑃𝑟
𝐻𝑅 2
𝜕𝑍 𝑑𝑃
= −𝑇𝑟 ∫ ( )
𝑅𝑇𝑐 0 𝜕𝑇𝑟 𝑃𝑟 𝑃𝑟
𝑃𝑟 𝑃𝑟
𝑆𝑅 𝜕𝑍 𝑑𝑃 𝑑𝑃
= −𝑇𝑟 ∫ ( ) − ∫ (𝑍 − 1)
𝑅 0 𝜕𝑇𝑟 𝑃𝑟 𝑃𝑟 0 𝑃𝑟

Calculated values of the quantities as determined by Lee and Kesler are given as functions
of Tr. and Pr.

𝐻 𝑅 (𝐻 𝑅 )° (𝐻 𝑅 )1
= +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐

𝑆 𝑅 (𝑆 𝑅 )° (𝑆 𝑅 )1
= +𝜔
𝑅 𝑅 𝑅

However, the generalized second-virial-coefficient correlation valid at low pressures forms

the basis for analytical correlations of the residual properties. The equation relating B to
the functions B0 and B1 is derived

Pitzer Correlations for Second Virial Coefficient

The generalized compressibility-factor correlation gave approximate
analysis expressions for limited range of pressures.
𝐵𝑃 𝑃𝑟
𝑍 = 1+ =1+Ḃ
𝑅𝑇 𝑇𝑟
𝐵𝑃𝑐
Ḃ=
𝑅𝑇𝑐
Second-virial-correlation yields the values for Ḃ:

Ḃ = 𝐵 ° + 𝜔𝐵1
Combining the two equations together,
𝐵𝑃𝑐
= 𝐵 ° + 𝜔𝐵1
𝑅𝑇𝑐
𝑃𝑟 𝑃𝑟
𝑍 = 1 + 𝐵° + 𝜔𝐵1
𝑇𝑟 𝑇𝑟
Perry’s HB Eq. 4-73

Since B, B⁰, and B1 are functions of T only,

 𝑃𝑐 𝑑𝐵 𝑑𝐵 ° 𝑑𝐵1
= +𝜔
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟 𝑑𝑇𝑟

Calculated values of the enthalpies and entropies are given as functions of Tr.

𝐻𝑅 𝑃 𝑑𝐵
= (𝐵 − 𝑇𝑟 )
𝑅 𝑅 𝑑𝑇𝑟

𝑆𝑅 𝑃 𝑑𝐵
=
𝑅 𝑅𝑇𝑐 𝑑𝑇𝑟
This equations result to:

𝐻𝑅 𝑑𝐵 ° 𝑑𝐵1
= 𝑃𝑟 (𝐵 ° − 𝑇𝑟 + 𝜔 (𝐵1 − 𝑇𝑟 ))
𝑅𝑇𝑐 𝑑𝑇𝑟 𝑑𝑇𝑟

𝑆𝑅 𝑑𝐵 ° 𝑑𝐵1
= 𝑃𝑟 ( +𝜔 )
𝑅 𝑑𝑇𝑟 𝑑𝑇𝑟

The dependence of B⁰ and B1 on reduced temperature is given by

0.422
𝐵 ° = 0.083 −
𝑇𝑟 1.6
Perry’s HB Eq. 4-77
0.179
𝐵1 = 0.139 −
𝑇𝑟 4.2
Perry’s HB Eq. 4-78

Correlations for the Third Virial Coefficient

Accurate data for third virial coefficients are far less common than for second virial
coefficients.

𝑍 = 1 + 𝐵𝜌 + 𝐶𝜌2
Equation for third virial coefficient is a function of ρ, molar density, = 1/V.

𝑃𝑟 𝑃𝑟 2
𝑍 =1+Ḃ + Ċ( )
𝑇𝑟 𝑍 𝑇𝑟 𝑍
Perry’s HB Eq. 4-94

𝐶𝑃𝑐 2
Ċ=
𝑅 2 𝑇𝑐 2
Pitzer-type correlation for Ċ can be written as

Ċ = 𝐶 ° + 𝜔𝐶 1
An expression for C⁰ as a function of reduced temperature is given by Orbey and Vera
0.02432 0.00313
𝐶 ° = 0.01407 + −
𝑇𝑟 𝑇𝑟 10.5
Perry’s HB Eq. 4-98
0.05539 0.00242
𝐶 1 = −0.02676 + 2.7 −
𝑇𝑟 𝑇𝑟 10.5
Perry’s HB Eq. 4-99

Calculation for path changes ΔH and ΔS

The generalized correlations for HR and SR , together with ideal-gas heat capacities, allow
calculation of enthalpy and entropy values of gases at any temperature and pressure.

Three Step Calculation Path

The actual path from state 1 to state 2
(dashed line) is replaced by a three-step
calculational path:

Step 1real to 1ideal: A hypothetical

process that transforms a real gas into
an ideal gas at T1 and P1. The enthalpy
and entropy changes for this process
are:
𝑖𝑔
𝐻1 − 𝐻1 = −𝐻1𝑅
𝑖𝑔
𝑆1 − 𝑆1 = −𝑆1𝑅

Step 1ideal to 2ideal: Changes in the ideal-gas state from (T1, P1) to (T2, P2). For this process,
𝑖𝑔 𝑖𝑔
∆𝐻 = 𝐻2 − 𝐻1
𝑇2
𝑖𝑔
∆𝐻 = ∫ 𝐶𝑝 𝑑𝑇
𝑇1

𝑖𝑔 𝑖𝑔
∆𝑆 = 𝑆2 − 𝑆1
𝑇2
𝑖𝑔 𝑑𝑇 𝑃2
∆𝑆 = ∫ 𝐶𝑝 − 𝑅 ln
𝑇1 𝑇 𝑃1

Step 2ideal to 2real: Another hypothetical process that transforms the ideal gas back into a
real gas at T2 and P2. Here,
𝑖𝑔
𝐻2 −𝐻1 = 𝐻2𝑅
𝑖𝑔
𝑆2 −𝑆1 = 𝑆2𝑅

For a change from state 1 to state 2,

𝑇1
𝑖𝑔 𝑖𝑔
𝐻1 = 𝐻0 + ∫ 𝐶𝑝 𝑑𝑇 + 𝐻1𝑅
𝑇0

𝑇2
𝑖𝑔 𝑖𝑔
𝐻2 = 𝐻0 + ∫ 𝐶𝑝 𝑑𝑇 + 𝐻2𝑅
𝑇0
The enthalpy change for the process, ΔH = H2 – H1, is the difference between these two
equations:
𝑇2
𝑖𝑔
∆𝐻 = ∫ 𝐶𝑝 𝑑𝑇 + 𝐻2𝑅 − 𝐻1𝑅
𝑇1

Similarly for entropy change,

𝑇2
𝑖𝑔 𝑑𝑇 𝑃2
∆𝑆 = ∫ 𝐶𝑝 − 𝑅 ln + 𝑆2𝑅 − 𝑆1𝑅
𝑇1 𝑇 𝑃1

Written alternative form these equations become:

𝑖𝑔
∆𝐻 = (𝐶𝑝 ) (𝑇2 − 𝑇1 ) + 𝐻2𝑅 − 𝐻1𝑅
𝐻

𝑖𝑔 𝑇2 𝑃2
∆𝑆 = (𝐶𝑝 ) ln − 𝑅 ln + 𝑆2𝑅 − 𝑆1𝑅
𝑆 𝑇1 𝑃1
Gas Mixtures
Although no theoretical basis exists for extension of generalized correlations to mixtures,
approximate results for mixtures can often be obtained with pseudocritical parameters
resulting from simple linear mixing rules according to the definitions:

𝜔 = ∑ 𝑦𝑖 𝜔𝑖
𝑖

𝑇𝑝𝑐 = ∑ 𝑦𝑖 𝑇𝑐𝑖
𝑖

𝑃𝑝𝑐 = ∑ 𝑦𝑖 𝑃𝑐𝑖
𝑖

The values so obtained are the mixture and pseudocritical temperature and pressure, Tpc
and Ppc which replace Tc, and Pc, to define pseudoreduced parameters:
𝑇
𝑇𝑝𝑟 =
𝑇𝑝𝑐
𝑃
𝑃𝑝𝑟 =
𝑃𝑝𝑐

Reference:
Smith, J.M. et al., Introduction to Chemical Engineering Thermodynamics 5th Edition
McGraw-Hill Companies, Inc, Singapore, 2001.

BATANGAS STATE UNIVERSITY

 College of Engineering, Architecture and Fine Arts
Gov. Pablo Borbon Campus II,
Alangilan, Batangas City, Philippines 4200
www.batstate-u.edu.ph Telefax: (043) 300-4044 locs. 106-108
CHEMICAL AND FOOD ENGINEERING DEPARTMENT

EXERCISES

Name:______________________________ Date:_______________________

Section:_____________________________ SR-Code:___________________

Solve the problems completely and box your final answer. Write your solution in a neat
and organized manner. Avoid too much erasure.

I.Thermodynamic Properties of Fluid

1. Estimate the change in enthalpy and entropy when liquid ammonia at 270 K is
compressed from its saturation pressure of 38 1 Wa to 1200 Wa. For saturated liquid
ammonia at 270 K, V' = 1.551 x x 10-3 m3 kg-1, and B = 2.095 x 10-3 K-1.

Solution:
T= 270 K P1 = 381 kPa
-3 3 -1
V= 1.511 x 10 m kg P2= 1200 kPa
-3 -1
B = 2.095 x 10 K
At constant T,
dS= -B(V)(P2-P1)
dH= (1-BT)(V)(P2-P1)
dS= -(2.095 x 10-3 K-10)( 1.511 x 10-3 m3 kg-1)( 1200-381)
dS= -2.661 J kg -1 K-1
dH= (1-(2.095 x 10-3 K-10 x 270 K)( 1.511 x 10-3 m3 kg-1)( 1200-381))
dH= 551.7 J kg -1

2. Liquid water at 298.15 K (25°C) and 1 bar fills a rigid vessel. If heat is added to the
water until its temperature reaches 323.15 K (50°C), what pressure is developed?
The average value of ,6 between 298.15 to 323.15 K (25 and 50°C) is 36.2 x 10-5
K-l. The value of K at 1 bar and 323.15 K (50°C) is 4.42 x10-5 bar-', and may be
assumed independent of P. The specific volume of liquid water at 298.15 K (25°C)
is 1.0030 cm3 g-1

Solution:
T1= 298.15 K k= 4.42 x 10-5 bar -1
T2 = 323.15 K P1= 1 bar
B= 36.2 x 10-5 K-1

For a constant-volume change,

B(T2-T1)-k(P2-P1) = 0
 36.2 x 10-5 K-1(323.15 K-298.15 K) -4.42 x 10-5 bar -1(P2- 1 bar)
P2= 205.75 bar

II.Two-Phase Systems and Thermodynamic Diagrams and Tables

1. Wet steam at 1100 kPa expands at constant enthalpy to 101.33 kPa, where its
temperature is 105°C. What is the quality of the steam in its initial state?

Solution:
From steam table,
At P1 = 1100 kPa, Hl = 781. 124 J/g, Hv = 2779.7 J/g
At P2 = 101.33 kPa and T2 = 105°C, H2 = 2686.1 J/g

For constant throttling,

H2 = Hl + (x) (Hv - Hl)
2686.1 = 781.124 + (x) (2779.7 – 781.124)
x = 0.953

2. Estimate the entropy change of vaporization of benzene at 50°C using Clausius-

Clapeyron equation.

Solution:
From Table 13-4 (Perry 8th ed),
A = 13.8858
B = 2788. 51
C = 220.79
B
ln Psat = A −
T+C
2788. 51
ln Psat = 13.8858 −
50 + 220.79
ln Psat = 36.166 kPa

B
Psat = 𝑒 A−T+C
𝑑𝑃𝑠𝑎𝑡 2788.51
= 𝑒 13.8858−50+220.79
𝑑𝑇
𝑑𝑃𝑠𝑎𝑡
= 1.375
𝑑𝑇
𝑅𝑇 𝑑𝑃𝑠𝑎𝑡
∆𝑆 =
𝑃 𝑑𝑇
(8.314) (323)
∆𝑆 = (1.375)
36.166

∆S = 102.14 J/mol.K
III. Generalized Property Correlation of Gases
1. Estimate V, HR, and SR for an equimolar mixture of carbon dioxide and propane
at 450 K and 140 bar by Lee/Kesler correlations.
Solution:
 Data:
For CO2: For C3H8
ω = 0.224 ω= 0.152
Tc = 304.2 K Tc = 369.8 K
Pc = 73.83 bar Pc = 42.48 bar
ω = y1ω1 + y2ω2 = (0.5)(0.224) + (0.5)(0.152) = 0.188
Tpc = y1Tc1 + y2Tc2 = (0.5)(304.2) + (0.5)(369.8) = 337 K
Ppc = y1Pc1 + y2Pc2 = (0.5)(73.83) + (0.5)(42.48) = 58.15 bar

450 𝐾
𝑇𝑝𝑟 = = 1.335
337 𝐾
140 𝑏𝑎𝑟
𝑃𝑝𝑟 = = 2.41
58.15 𝑏𝑎𝑟

From Table 2-351 and 2-352,

Z0 = 0.697
Z1 = 0.205

𝑍 = 𝑍 ° + 𝜔𝑍1
𝑍 = 0.697 + (0.188)(0.205) = 0.736
𝑐𝑚3 𝑏𝑎𝑟
𝑍𝑅𝑇 (0.736)(83.14 𝑚𝑜𝑙 𝐾 )(450 𝐾) 𝒄𝒎𝟑
𝑉= = = 𝟏𝟗𝟔. 𝟕
𝑃 140 𝑏𝑎𝑟 𝒎𝒐𝒍
° °
(𝐻 𝑅 ) (𝑆 𝑅 )
= −1.730 = −0.967
𝑅𝑇𝑝𝑐 𝑅

1 1
(𝐻 𝑅 ) (𝑆 𝑅 )
= −0.169 = −0.330
𝑅𝑇𝑝𝑐 𝑅

𝐻 𝑅 (𝐻 𝑅 )° (𝐻 𝑅 )1
= +𝜔
𝑅𝑇𝑐 𝑅𝑇𝑐 𝑅𝑇𝑐
= −1.730 + (0.188)(−0.169) = −1.762
𝑱
𝐻 𝑅 = (−1.762)(8.314)(337) = −𝟒, 𝟗𝟑𝟕
𝒎𝒐𝒍
𝑆 𝑅 (𝑆 𝑅 )° (𝑆 𝑅 )1
= +𝜔
𝑅 𝑅 𝑅
= −0.967 + (0.188)(−0.330) = −1.029
𝑱
𝑆 𝑅 = (−1.029)(8.314) = −𝟖. 𝟓𝟔
𝒎𝒐𝒍 𝑲

2. Estimate volume for tetrafluoroethane at 400 K and 15 bar by appropriate

generalized correlations.

Solution:
Data:
ω = 0.327
Tc = 374.2 K
 Pc = 40.60 bar

400 𝐾
𝑇𝑟 = = 1.069
374.2 𝐾
15 𝑏𝑎𝑟
𝑃𝑟 = = 0.369
40.60 𝑏𝑎𝑟
0.422 0.422
𝐵 ° = 0.083 − 1.6 = 0.083 − = −0.296
𝑇𝑟 1.0691.6
0.179 0.179
𝐵1 = 0.139 − = 0.139 − = 0.00375
𝑇𝑟 4.2 1.0694.2
𝑃𝑟 𝑃𝑟 0.369 0.369
= 1 + 𝐵° + 𝜔𝐵1 = 1 + (−0.296) ( ) + (0.327)(0.00375) = 0.898
𝑇𝑟 𝑇𝑟 1.069 1.069
𝑐𝑚3 𝑏𝑎𝑟
𝑍𝑅𝑇 (0.898)(83.14 )(400 𝐾) 𝒄𝒎𝟑
𝑉= = 𝑚𝑜𝑙 𝐾 = 𝟏, 𝟗𝟗𝟎. 𝟗𝟑
𝑃 15 𝑏𝑎𝑟 𝒎𝒐𝒍

BATANGAS STATE UNIVERSITY

College of Engineering, Architecture and Fine Arts
 Gov. Pablo Borbon Campus II,
Alangilan, Batangas City, Philippines 4200
www.batstate-u.edu.ph Telefax: (043) 300-4044 locs. 106-108
CHEMICAL AND FOOD ENGINEERING DEPARTMENT

EXERCISES

Name:______________________________ Date:_______________________

Section:_____________________________ SR-Code:___________________

GENERAL INSTRUCTIONS: Follow the instructions for each part carefully.

PART I. MULTIPLE CHOICE

Select the best answer.

1. Which of the following relation is correct?

a) dU=TdS-pdV
b) dH=TdS+Vdp
c) dG=Vdp-SdT
d) all of the mentioned
2. Which of the following is not a Maxwell equation?
a) (∂T/∂V) = -(∂p/∂S)
b) (∂T/∂p) = -(∂V/∂S)
c) (∂p/∂T) = (∂S/∂V)
d) (∂V/∂T) = -(∂S/∂p)
3. A pure substance which exists in a single phase has ____ independent variables.
a) zero
b) one
c) two
d) three
4. For getting TdS equations, we assume entropy to be a function of T and V and
also of T and p.
a) true
b) false
5. The first TdS equation is
a) TdS=Cv*dT + T(∂T/∂p)dV
b) TdS=Cv*dT – T(∂p/∂T)dV
c) TdS=Cv*dT + T(∂p/∂T)dV
d) TdS=Cv*dT – T(∂T/∂p)dV
6. ∆Hlv decreases monotonically with ________ temperature from the triple point to
the critical point, where it becomes zero.
a. decreasing b. constant c. increasing

7. A phase diagram shows the relationship between

a. Pressure, volume, and three phases of matter
b. Temperature, pressure, and three phases of matter
c. Temperature, volume, and three phases of matter
8. The lines on a phase diagram represent the temperatures and pressures at which
a. One phase of the substance is present
b. Two phase of the substance is present
c. Three phase of the substance is present
9. The type of diagram most frequently used to analyze energy transfer system cycles
a. TS diagram b. PH diagram c. HS diagram

10. The type of diagram frequently used for performance calculation of a refrigerating
machine
a. TS diagram b. PH diagram c. HS diagram

11. The type of diagram used when quality is greater than 50% and for superheated
steam
a. TS diagram b. PH diagram c. HS diagram

12. When a system consists a __________ and __________ phases coexisting in

equilibrium, the total value of any extensive property of the two-phase system is
the sum of the total properties of the phases
a. Superheated liquid and superheated vapor
b. Subcooled liquid and saturated vapor
c. Saturated liquid and saturated vapor
13. A phase transition at _______ temperature and pressure occurs whenever one of
the curves is crossed
a. decreasing b. constant c. increasing

14. Thermodynamic diagrams usually show a net of ifferent lines which includes the
following except
a. isobars b. isotherms c. isochors

15. Which of the following is the integrated form of Clausius-Clapeyron equation

𝑷𝟐 𝝀𝒗 (𝑻𝟐−𝑻𝟏)
a. 𝟐. 𝟑 𝒍𝒐𝒈 =
𝑷𝟏 𝑹𝑻𝟏𝑻𝟐
𝑃1 𝜆𝑣 (𝑇2−𝑇1)
b. 2.3 log 𝑃2 = 𝑅𝑇1𝑇2
𝑃2 𝜆𝑣 (𝑇2−𝑇1)
c. 2.3 𝑙𝑜𝑔 =
𝑃1 𝑇1𝑇2
16. Under which one of the following conditions do real gases approach the ideal gas
behavior?
A. Low Temperature and High Pressure
B. High Temperature and High Pressure
C. High Temperature and Low Pressure
17. What is the value of Z for ideal gases?
A. < 1
B. > 1
C. 1
18. A real gas
A. Does not obey all the assumptions of the kinetic-molecular theory
B. Consists of particles that do not occupy space
C. Cannot be produced in scientific laboratories
19. An ideal gas is a hypothetical gas
A. Not made of particles
B. That conforms to all of the assumptions of the kinetic theory
C. Made of motionless particles
 20. What is absolute zero?
A. -459.67 ⁰F
B. -459.67 ⁰C
C. 0 ⁰C

PART II. PROBLEM SOLVING

Solve the problems completely and box your final answer. Write your solution in a neat
and organized manner.

1. Determine the enthalpy and entropy changes of liquid water for a change of state
from 1 bar and 25 ℃ to 1,000 bar and 50℃. The following data for water are
available:

Solution:
dH= Cp(T2-T1)-(1-BT2)V(P2-P1)
dS= Cp ln(T2/T1) -BV(P2-P1)
For P= 1 bar,
Cp=(75.305+75.314)/2 = 75.310J mol-1K-1
For T= 50 C
V= (18.234+18.174)/2 = 18.204 cm3 mol-1
B= (458+568)/2 x 10-6 = 513 x 10-6 K-1
By substituting this values to the equation, we obtain,
dH= 3400 J/mol
dS= 5.13 J/mol K

2. Find the change in entropy if 500 g of water at 80o C is added to 300 g of water at
20o C.

Solution:
The total amount of water is 800g, so the final temperature of the system is given
by:
(5/8) 353K + (3/8) 293K = 330.5K
For m1= 500 g and m2=300g, the entropy change is given by
dS= ∫dQ/T
dS =

dS= 1cal/(gK) (m1 ln 330.5/353 + m2 ln 330.5/293)

dS = 3.20 cal/K
3. Calculate the volume and the enthalpy content of a steam at 120°C and 80% quality.

Solution:
From steam table,
Vl = 0.001063 m3/kg
 Vv = 0.8919 m3/kg
Hl = 503.71 kJ/kg
Hv = 2706.3 kJ/kg
H = (1 – xv2) Hl2 + xv2 Hv2
H = (1-0.8) (503.71) + (0.8) (2706.3)

H = 2265.78 kJ/kg
V = (1 – xv2) Vl2 + xv2 Vv2
V = (1-0.8) (0.001063) + (0.8)(0.8919)

V = 0.7137 m3/kg

4. The latent heat of vaporization at 100°C is 539 kcal/kg. Calculate the boiling point
of water at 600 mm Hg. The value of the universal gas constant is 1.98 cal/mol.K.

Solution:
We use the integrated form of Clausius Clapeyron equation:
539 kcal 18 kg
λv = x
kg kmol

𝜆𝑣 = 9702 𝑐𝑎𝑙/𝑚𝑜𝑙
P2 λv (T2 − T1)
2.3 log =
P1 RT1T2
600 9702 (T2 − 373)
2.3 log =
760 (1.98)(373)T2

T2 = 366.5 K
5. Wet steam at 230°C has a density of 0.025 g/cm3. Determine x, H, and S.

Solution:
From steam table,
Vl = 1.209 cm3/g
Vv = 71.45 cm3/g
Hl = 990.3 J/g
Hv = 2802.0 J/g
Sl = 2.6102 J/g.K
Sv = 6.2107 J/g.K
V = (1 – x) Vl2 + x Vv2
1/0.025 = (1-x) (1.209) + (x) (71.45)

x = 0.552
H = (1 – x) Hl2 + x Hv2
H = (1-0.552) (990.3) + (0.552) (2802.0)

H = 1991 J/g
S = (1 – x) Sl2 + x Sv2
 S = (1-0.552) (2.6102) + (0.552) (6.2107)

S = 4.559 J/g.K
6. The compressibility factor for definite amount of a Van der Waals’ gas at 0⁰C and
100 atm is found to be 0.5. Assuming the volume of gas molecules is negligible,
the Van der Waals’ constant ‘a’ for a gas is:

𝐿 𝑎𝑡𝑚
𝑍𝑅𝑇 (0.5) (0.08206 𝑚𝑜𝑙 𝐾 ) (273.15 𝐾) 𝐿
𝑉= = = 0.112073445
𝑃 100 𝑎𝑡𝑚 𝑚𝑜𝑙
𝑛 2 𝑉
[𝑃 + 𝑎 ( ) ] ( − 𝑏) = 𝑅𝑇
𝑉 𝑛
2
1 𝐿 𝑎𝑡𝑚
[100 𝑎𝑡𝑚 + 𝑎 ( ) ] (0.112073445) = (0.08206 ) (273.15 𝐾)
0.112073445 𝑚𝑜𝑙 𝐾

𝒃 = 𝟏. 𝟐𝟓𝟔

7. Determine the molar volume of n-butane at 510 K and 25 bar by generalized

compressibility factor correlation

Tc = 425.1 K
Pc = 37.96 bar
510 𝐾
𝑇𝑟 = = 1.2
425.1 𝐾
25 𝑏𝑎𝑟
𝑃𝑟 = = 0.659
37.96 𝑏𝑎𝑟
Z⁰ = 0.869
Z1 = 0.038
Ω = 0.200

𝑍 = 𝑍 ° + 𝜔𝑍1
𝑍 = 0.865 + (0.2)(0.038) = 0.873
𝑐𝑚3 𝑏𝑎𝑟
𝑍𝑅𝑇 (0.873)(83.14 )(510 𝐾) 𝒄𝒎𝟑
𝑉= = 𝑚𝑜𝑙 𝐾 = 𝟏, 𝟒𝟖𝟎. 𝟕
𝑃 25 𝑏𝑎𝑟 𝒎𝒐𝒍

8. Determine the molar volume of n-pentane at 500 K and 10 bar by appropriate

generalized correlations.
Data
ω = 0.252
Tc = 469.7 K
Pc = 33.70 bar

500 𝐾
𝑇𝑟 = = 1.065
469.7 𝐾
10 𝑏𝑎𝑟
𝑃𝑟 = = 0.297
33.70 𝑏𝑎𝑟
0.422 0.422
𝐵 ° = 0.083 − 1.6 = 0.083 − = −0.299
𝑇𝑟 1.0651.6
 0.179 0.179
𝐵1 = 0.139 − 4.2 = 0.139 − = 0.0016
𝑇𝑟 1.0654.2
𝑃𝑟 𝑃𝑟 0.297 0.297
𝑍 = 1 + 𝐵° + 𝜔𝐵1 = 1 + (−0.299) ( ) + (0.252)(0.0016) = 0.917
𝑇𝑟 𝑇𝑟 1.065 1.065
𝑐𝑚3 𝑏𝑎𝑟
𝑍𝑅𝑇 (0.917)(83.14 𝑚𝑜𝑙 𝐾 )(500 𝐾) 𝒄𝒎𝟑
𝑉= = = 𝟑, 𝟖𝟏𝟎. 𝟖𝟒
𝑃 10 𝑏𝑎𝑟 𝒎𝒐𝒍

9. Estimate the Z for benzene and cyclohexane equimolar mixture at 650 K and 60
bar by the Lee Kresler correlations.

Data:
For Benzene:
ω = 0.210
Tc = 562.2 K
Pc = 48.98 bar
For Cyclopentane:
ω= 0.210
Tc = 553.6 K
Pc = 40.73 bar

ω = y1ω1 + y2ω2 = (0.5)(0.210) + (0.5)(0.210) = 0.210

Tpc = y1Tc1 + y2Tc2 = (0.5)(562.2) + (0.5)(553.6) = 557.90 K
Ppc = y1Pc1 + y2Pc2 = (0.5)(48.98) + (0.5)(40.73) = 44.855 bar

650 𝐾
𝑇𝑝𝑟 = = 1.165
557.9 𝐾
60 𝑏𝑎𝑟
𝑃𝑝𝑟 = = 1.338
44.855 𝑏𝑎𝑟

From Table 2-351 and 2-352,

Z0 = 0.6543
Z1 = 0.1219

𝑍 = 𝑍 ° + 𝜔𝑍1
𝑍 = 0.6543 + (0.210)(0.1219) = 𝟎. 𝟔𝟕𝟗𝟗

10. What pressure is generated when 1 lb mol of methane is stored in a volume of 2 ft3
at 122⁰F based on a generalized correlation?

Data
Pr = 4.14
Tr = 1.695
ω = 0.012
Z0 = 0.887
Z1 = 0.258
𝑍 = 0.887 + (0.012)(0.258) = 0.890
 𝑓𝑡 3 𝑎𝑡𝑚
𝑍𝑅𝑇 (0.890)(0.7302 )(581.67 𝑅)
𝑃= = 𝑚𝑜𝑙 𝑅 = 𝟏𝟖𝟗 𝒂𝒕𝒎
𝑉 2 𝑓𝑡 3