Chapter 29

Properties

NOMENCLATURE
a length of base edge
b width of base measured perpendicular to plane a
c carbon number of the hydrocarbon
DAB diffusion coefficient (cm2/s)
d diameter
dF foam density (lb/ft3)
dL liquid density (lb/ft3)
dV vapor density (lb/ft3)
h height measured perpendicular to plane ab
P vapor pressure (mm Hg)
P pressure (atm)
S solubility, mole fraction
s specific surface ¼ particle surface per unit volume of bed
t temperature (°C)
u superficial vapor velocity (ft/s)
V volume of shape
Wi mass fraction of pure component i
Z compressibility factor
d volume fraction of liquid phase
y kinematic viscosity (mm2/s (¼ cSt))
m dynamic viscosity (mPa s (¼ .001 g/mm s, ¼ cP))
mi viscosity of pure component i
mmix mixture viscosity
« fractional free volume, dimensionless
w shape factor ¼ area of sphere divided by the surface area of a particle of equal volume
r density (g/cm3)
s surface tension
a, b regression constants
d volume fraction of liquid phase

INTRODUCTION
This chapter provides a variety of physical properties, correlations, and conversion factors that may be difficult to find
elsewhere. They range from approximations that are useful for quick conceptual calculations to the precise equations-
of-state for water and steam.
Properties for pure compounds are readily available in handbooks and on the web. It is more difficult to find correlation
coefficients for temperature-dependent properties such as viscosity and vapor pressure. If accurate values at three temper-
atures are known for these properties, it is easy to write equations that fit the three points that are quite sufficient for general
process design; the procedures are given in this chapter.
Properties for natural substances (e.g., foods and oils) may vary significantly depending on the source of the material
and its purity. Major properties can be found in specialty handbooks and are sometimes available from the equipment man-
ufacturers who specialize in processing the materials.
Visual basic for application (VBA) functions are included in the accompanying Excel workbook for

Rules of Thumb for Chemical Engineers. http://dx.doi.org/10.1016/B978-0-12-811037-9.00029-1

© 2018 Elsevier Inc. All rights reserved. 463
464 Rules of Thumb for Chemical Engineers

l Computing the relative humidity (RH) of air, given atmospheric pressure, dry-bulb temperature, and wet-bulb
temperature.
l Solving the International Association for the Properties of Water and Steam (IAPWS) correlations for density, enthalpy,
entropy, heat capacity, viscosity, thermal conductivity, boiling point, and vapor pressure of saturated water and steam.
l Estimating a gas compressibility factor using the Redlich–Kwong equation of state.
l Estimating the equilibrium solubility of inorganic gases in petroleum liquids.
When undertaking a new project, it can save time to compile physical properties for the materials that will be used,
including all of the process streams that will appear on material and flow balances and utilities. A datasheet is provided
to help organize the data.

APPROXIMATE PHYSICAL PROPERTIES

Gravity of a boiling hydrocarbon liquid mixture at all pressures:
4 lb/gal or 30 lb/ft3 use Tables 29.1 and 29.2 to estimate liquid density when the molar concentrations are known.

TABLE 29.1 Liquid-Volume Contribution of Dissolved Gases in Hydrocarbon Mixtures

Component MW L/kg mol Gal/lb mol
O2 32 28.1 3.37
CO 28 34.9 4.19
CO2 44 53.1 6.38
SO2 64 45.8 5.50
H2S 34 43.1 5.17
N2 28 34.6 4.16

H2 2 28.1 3.38

TABLE 29.2 Liquid-Volume Contribution of Light Hydrocarbons in Hydrocarbon Mixtures

Component MW L/kg mol Gal/lb mol
C1 16 53.3 6.4
C¼
2 30 84.3 10.12
C2 28 80.3 9.64
C¼
3 44 86.8 10.42
C3 42 80.5 9.67
iC4 58 103.1 12.38

nC4 58 99.4 11.93

iC5 72 115.3 13.85
nC5 72 114.2 13.71
iC6 86 129.1 15.50
C6 86 129.7 15.57
iC7 100 143.2 17.2

C7 100 145.4 17.46

C8 114 161.5 19.39
 Properties Chapter 29 465

The higher heating value (HHV) is defined as the amount of heat released from a fuel at 25°C once it is combusted and the
products of combustion have returned to 25°C. This accounts for the heat of vaporization of water (as a combustion product)
and assumes that the water returns to the liquid state (Tables 29.3–29.5).
Assumed gravities used commercially in determining rail tariffs:
Propane or butane 4.7 lb/gal
Natural gasoline 6.6 lb/gal
Volume of a “perfect gas”:
379 ft3/lb mol at 60°F and 14.7 psia, or 22.4 L/g mol at 0°C and 1 atm (101.325 kPa)
This volume is directly proportional to the absolute temperature ¼ °F plus 459.67°, or °C + 273.15°. It is inversely propor-
tional to the absolute pressure.
Molal heat of vaporization at the normal boiling point (1 atm):
8000 cal/g mol or 14,400 Btu/lb mol
The latent heat of water is about five times that for an organic liquid.
Heat capacities, Btu/lb °F (kJ/kg °C)
Water 1.0 (4.2)
Steam/hydrocarbon vapors 0.5 (2.1)
Air 0.25 (1.0)
Solids 0.25 (1.0)
For structural strength,
Weight of concrete ¼ weight of equipment supported

TABLE 29.3 Higher Heating Values of Solid Fuels

Solid Fuel HHV (MJ/kg) HHV (Btu/lb)
Low volatile bituminous coal and high volatile anthracite coal 25.5–32.5 11,000–14,000

Subbituminous coal 20.9–25.5 9000–11,000

Lignite 16.3–18.6 7000–8000
Coke and coke breeze 27.9–30.2 12,000–13,000
Wood 18.6–20.9 8000–9000
Bagasse (dry) 16.3–20.9 7000–9000

TABLE 29.4 Higher Heating Values of Gaseous Fuels

Gaseous Fuel HHV (MJ/scm) HHV (Btu/scf)
Coke oven gas 18.6–26.1 500–700
Blast furnace gas 3.4–4.5 90–120
Natural gas 33.5–48.4 900–1300

Refinery off–gas 41.0–74.5 1100–2000

Hydrogen 141.9 3808
466 Rules of Thumb for Chemical Engineers

TABLE 29.5 Higher Heating Values of Liquid Fuels

Liquid Fuel HHV (MJ/m3) HHV (Btu/gal)

Heavy crude (14°API) 41,800 150,000
Light crude (30°API) 39,000 140,000
Fuel oils
No. 1 38,300 137,400
No. 2 38,900 139,600

No. 3 39,500 141,800

No. 4 40,400 145,100
No. 5 41,500 148,800
No. 6 42,500 152,400
15°API 49,800 178,710
Kerosene (45°API) 44,300 159,000

Gasoline (60°API) 41,800 150,000

Naphtha (65°API) 32,100 115,000
Butane 28,800 103,300
Propane 25,500 91,600
Ethane 18,400 66,000

For desert landscaping (home or office)—contractors use

yards (yds3) rock ¼ ft2 covered/100
For water analysis, 1 mg/L ¼ 1 ppm
Source for this section: Ref. [1]

VAPOR-PRESSURE EQUATION
The Antoine Equation is often used to model vapor pressure.
B
Log 10 ðPÞ ¼ A  (29.1)
C+t
where
P ¼ vapor pressure (mm Hg)
t ¼ temperature (°C)
A, B, C are coefficients
The accuracy of the expression is related to the behavior of the liquid- and the vapor-pressure range being modeled.
Rather than regress a large number of data points, coefficients can be calculated directly from three known values of vapor
pressure. Over a range of 1–760 mm Hg, the accuracy is usually within 3%, for all types of liquids—even mixtures. With a
wider range, to 30 atm, the accuracy is often within 5%.
Here is how to compute the constants, with the three data points termed as P1, t1, P2, t2, and P3, t3. An intermediate
calculation simplifies the expression to obtain the coefficient C.


P2
Log 10 ðt1  t2 Þ
P
X¼
3
P1
Log 10 ðt2  t3 Þ
P2
 Properties Chapter 29 467

t1  ðt3 XÞ
C¼
X1


P2
Log 10
P3
B¼
1=ðt3 + CÞ  1=ðt2 + CÞ
B
A ¼ Log 10 ðP2 Þ
t2 + C

Example
Vapor-pressure values for toluene are listed in Table 29.6. Using the data points for vapor pressures 1, 400, and 30,400 mm Hg,
X ¼ 0.365975
C ¼ 226.25
B ¼ 1410.9
A ¼ 7.0705
Vapor-pressure values predicted by the equation are compared with the published values at each value. The maximum dif-
ference of 2.74% at 5 mm Hg could indicate a slight error in the published values rather than a failure of the correlation. When
the exercise is repeated using the data point for vapor pressure 5 mm Hg instead of 1 mm Hg, the maximum error is reduced to
1.21%. Notice that the predicted values exactly match the source data at the three vapor-pressure points used to calculate the
parameters.

TABLE 29.6 Vapor Pressure of Toluene

Published Data Predicted From Equation
Vapor Pressure (mm Hg) Temperature (°C) Vapor Pressure (mm Hg) Difference
1.0 26.7 1.0 0.00%
5.0 4.4 5.1 2.74%
10.0 6.4 10.1 1.38%
20.0 18.4 20.1 0.55%
40.0 31.8 40.1 0.19%
60.0 40.3 59.9 0.20%

100.0 51.9 99.5 0.46%

200.0 69.5 199.5 0.26%
400.0 89.5 400.0 0.00%
760.0 110.6 762.0 0.26%
1520.0 136.5 1517.1 0.19%
3800.0 178.0 3804.7 0.12%

7600.0 215.8 7564.3 0.47%

15,200.0 262.5 15,266.5 0.44%
22,800.0 292.8 22,503.9 1.30%
30,400.0 319.0 30,400.0 0.00%
468 Rules of Thumb for Chemical Engineers

LIQUID VISCOSITY
Dynamic (or Absolute) Viscosity
Water at 20.2°C (68.4°F) has an absolute viscosity of 1 cP.

Kinematic Viscosity
Kinematic viscosity is the ratio of dynamic viscosity to density.
m
u¼ (29.2)
r
where
u ¼ kinematic viscosity (mm2/s (¼ cSt))
m ¼ dynamic viscosity (mPa s (¼ 0.001 kg/m s, ¼ cP))
r ¼ density (g/cm3)

Example
Ethylene glycol at 20°C is approximately 12 cP and 1.11 g/cm3, therefore
u ¼ (0.012 g/mm)/[1.11 g/cm3  (1 cm3/1000 mm3)]
¼ 10.8 cSt

Viscosity of Mixtures
For nonpolar mixtures, the following equation gives mixture viscosity usually within 5% to 10% [2]. Do not use with
polar compounds, including water.
X
lnðmmix Þ ¼ Wi lnðmi Þ (29.3)
where
mmix ¼ mixture viscosity
mi ¼ viscosity of pure component i
Wi ¼ mass fraction of pure component i

Emulsions
The viscosity of an emulsion of nonmiscible liquids can be estimated with [3]


mC 1:5mD dD
m ¼ 1+ (29.4)
dC mD + mC
where
m ¼ viscosity, any units
d ¼ volume fraction of liquid phase
Subscripts
D ¼ dispersed phase
C ¼ continuous phase
The relationship is valid for the following ranges of variables:
Viscosity of continuous phase ¼ 0.5–50 cP
 Properties Chapter 29 469

Viscosity of dispersed phase ¼ 0.5–100 cP

Volume fraction of continuous phase ¼ 0.1–1.0
Volume fraction of dispersed phase ¼ 0.0–0.9

Saybolt Universal Seconds

An obsolete method for measuring kinematic viscosity in the petroleum industry is by use of the Saybolt Viscometer. The
method, described in ASTM D88-07 [4], measures the time for 60 mL of a petroleum product to flow through an orifice at a
controlled temperature. The result is expressed in terms of Saybolt Universal Seconds (SUS) and Saybolt Furol Seconds
(SFS). ASTM D2161-05e1 [5] establishes the equations relating SUS and SFS to SI kinematic viscosity units (mm2/s).

RELATIVE HUMIDITY
Here is an equation for RH [6] and a short VBA function subroutine that enhances its value. The average difference between
the equation and actual values runs only 0.33 percentage points and the highest absolute difference seen in comparisons was
2 percentage points.
100ðPw  Pm Þ
RH ¼ (29.5)
Pd
where
Pd ¼ Pc 10Kd ð1Tc =Td Þ
Pw ¼ Pc 10Kw ð1T


c =Tw Þ

Tw  491:67
Pm ¼ 0:000367 1 + Pb ðTd  Tw Þ
1571
Kd and Kw are functions of dry-bulb and wet-bulb temperatures, Td and Tw.
Function RH(Td, Tw, Pb)
’ calculates relative humidity
’ Source: Pallady, P.H., "Compute Relative Humidity Quickly"
’ Chemical Engineering, November 1989, p. 255.
’
’ Td = Dry-bulb temperature, deg C – see comment below
’ Tw = Wet-bulb temperature, deg C – see comment below
’ Pb = Atmospheric pressure, mm Hg
’
’ Convert temperatures to absolute, deg R
’ If inputs are in deg F instead of deg C, then omit the next two lines
Td = Td * 1.8 + 32 ’converts to deg F
Tw = Tw * 1.8 + 32 ’converts to deg F
Td = Td + 459.67 ’converts to deg R
Tw = Tw + 459.67 ’converts to deg R

’ Constants
PC = 166818 ’critical Pressure, mm Hg
TC = 1165.67 ’critical Temperature, deg R
’ Correlation coefficients
C0 = 4.39553
C1 = -0.0034691
C2 = 0.0000030721
C3 = -0.00000000088331
K0 = 0.000367
K1 = 1571
K2 = 491.67
470 Rules of Thumb for Chemical Engineers

’ Calculate Kd and Kw
Kd = C0 + C1 * Td + C2 * Td ^2 + C3 * Td ^3
Kw = C0 + C1 * Tw + C2 * Tw ^2 + C3 * Tw ^3

’ Calculate Pd, Pw, and Pm

Pd = PC * 10 ^(Kd * (1 - TC / Td))
Pw = PC * 10 ^(Kw * (1 - TC / Tw))
Pm = K0 * (1 + (Tw - K2) / K1) * Pb * (Td - Tw)

’ Calculate Relative Humidity

RH = 100 * ((Pw - Pm) / Pd)

’ Check to see if RH is in the range of 0 to 100

’ If not, set to the limits
If RH < 0 Then RH = 0
If RH > 100 Then RH = 100

End Function

Nomenclature
K ¼ temperature-dependent parameter, dimensionless; Kd ¼ value at Td; Kw ¼ value at Tw
P ¼ pressure of water vapor at any temperature T(R) (mm Hg)
Pb ¼ barometric pressure (mm Hg)
Pc ¼ critical pressure of water (166,818 mm Hg)
Pd ¼ saturation pressure of water at the dry-bulb temperature (mm Hg)
Pm ¼ partial pressure of water vapor due to solution depression (Td  Tw) (mm Hg)
PW ¼ saturation pressure of water at the wet-bulb temperature (mm Hg)
RH ¼ relative humidity (%)
Tc ¼ Critical temperature of water ¼ 1165.67 R
Td ¼ dry-bulb temperature (R)
Tw ¼ dry-bulb temperature (R)

SURFACE TENSION
For a liquid with known critical temperature and surface tension at one temperature, use this equation to estimate its surface
tension at other temperatures [7]. It is accurate within a few percent for nonpolar compounds in regions well removed from
the critical point. For polar liquids, the exponent 1.2 may be as small as 1.0.


TC  T2 1:2
s2 ¼ s1 (29.6)
TC  T1

THERMODYNAMIC PROPERTIES OF WATER AND STEAM

IAPWS published a set of correlations that give properties for water and steam throughout the range from the melting-
pressure curve to 1273 K at pressures to 1000 MPa [8]. Agreement with experimental data ranges from 0.1% to about
2% depending on the property and the temperature and pressure at which it is evaluated. IAPWS gives charts that map the
uncertainties.
Owing to the large number of coefficients, the correlations require a computer for efficient evaluation. Spang wrote a set
of VBAs function subroutines that solve the IAPWS equation set as a function of temperature and pressure [9].
Spang’s VBA functions are located on the Rules of Thumb for Chemical Engineers Excel Spreadsheets. The function
calls are listed in Table 29.7.

GAS DIFFUSION COEFFICIENTS

Owing to the scarcity of reliable experimental data, investigators have developed various methods for estimating binary gas
diffusion coefficients. The one by Singh and Singh [10] requires input data that are easy to find. Comparisons with known
 Properties Chapter 29 471

TABLE 29.7 VBA Functions for Water and Steam Properties

Property VBA Function

Density, single phase (kg/m ) 3
¼densW (T, P)
Specific internal energy, single phase (kJ/kg) ¼energyW (T, P)
Specific enthalpy, single phase (kJ/kg) ¼enthalpyW (T, P)
Specific entropy, single phase (kJ/kg) ¼entropyW (T, P)
Specific isobaric heat capacity, single phase (kJ/(kg K)) ¼cpW (T, P)

Specific isochoric heat capacity, single phase (kJ/(kg K)) ¼cvW (T, P)
Dynamic viscosity, single phase (Pa s) ¼viscW (T, P)
Thermal conductivity, single phase (W/(m K)) ¼thconW (T, P)
Boiling point as a function of pressure (K) ¼tSatW (P)
Vapor pressure, bar absolute ¼pSatW (T)
3
Density in saturation state (kg/m )
Boiling water as a function of temperature ¼densSatLiqTW (T)
Boiling water as a function of pressure ¼densSatLiqPW (P)
Saturated steam as a function of temperature ¼densSatVapTW (T)
Saturated steam as a function of pressure ¼densSatVapPW (P)

Specific internal energy in saturation state (kJ/kg)

Boiling water as a function of temperature ¼energySatLiqTW (T)
Boiling water as a function of pressure ¼energySatLiqPW (P)
Saturated steam as a function of temperature ¼energySatVapTW (T)
Saturated steam as a function of pressure ¼energySatVapPW (P)

Specific enthalpy in saturation state (kJ/kg)

Boiling water as a function of temperature ¼enthalpySatLiqTW (T)
Boiling water as a function of pressure ¼enthalpySatLiqPW (P)
Saturated steam as a function of temperature ¼enthalpySatVapTW (T)
Saturated steam as a function of pressure ¼enthalpySatVapPW (P)
Specific entropy in saturation state (kJ/kg)
Boiling water as a function of temperature ¼entropySatLiqTW (T)
Boiling water as a function of pressure ¼entropySatLiqPW (P)
Saturated steam as a function of temperature ¼entropySatVapTW (T)
Saturated steam as a function of pressure ¼entropySatVapPW (P)
Specific isobaric heat capacity in saturation state (kJ/(kg K))
Boiling water as a function of temperature ¼cpSatLiqTW (T)
Boiling water as a function of pressure ¼cpSatLiqPW (P)
Saturated steam as a function of temperature ¼cpSatVapTW (T)
Saturated steam as a function of pressure ¼cpSatVapPW (P)
Specific isochoric heat capacity in saturation state (kJ/(kg K))
Boiling water as a function of temperature ¼cvSatLiqTW (T)
Boiling water as a function of pressure ¼cvSatLiqPW (P)
Saturated steam as a function of temperature ¼cvSatVapTW (T)
Saturated steam as a function of pressure ¼cvSatVapPW (P)
Dynamic viscosity in saturation state (Pa s)
Boiling water as a function of temperature ¼viscSatLiqTW (T)
Boiling water as a function of pressure ¼viscSatLiqPW (P)
Saturated steam as a function of temperature ¼viscSatVapTW (T)
Saturated steam as a function of pressure ¼viscSatVapPW (P)
Thermal conductivity in saturation state (W/(m K))
Boiling water as a function of temperature ¼thconSatLiqTW (T)
Boiling water as a function of pressure ¼thconSatLiqPW (P)
Saturated steam as a function of temperature ¼thconSatVapTW (T)
Saturated steam as a function of pressure ¼thconSatVapPW (P)

Arguments are temperature (K) and pressure (bar, absolute). “Single phase” may be liquid water or gaseous steam, but not a mixture. An answer of “1” is
returned if the input data are outside the allowable or applicable range.
472 Rules of Thumb for Chemical Engineers

data and other correlations show it to have an average error of 17.3%. The authors say that experimental data are difficult to
obtain and it is often 5%–10% erroneous.


1:622 1 1 0:5
T +
MA MB
DAB ¼ 2790  2 (29.7)
P VA 1=3 + VB 1=3
where
DAB ¼ diffusion coefficient (cm2/s)
T ¼ temperature (K)
P ¼ pressure (atm)
MA, MB ¼ molecular weight
VA, VB ¼ molecular volume at the normal boiling point (from boiling point density) (cc/gmol)
If the diffusion coefficient at one temperature is known, the coefficient at another temperature is found with

1:622
D1 T1
¼ (29.8)
D0 T0

BULK MODULUS
Values for bulk modulus, a measure of a fluid’s compressibility, are listed in Table 29.8.

WATER AND HYDROCARBONS

Water in Natural Gas
Fig. 29.1 shows water content of lean, sweet natural gas. It can be used also for gases that have as much as 10% CO2 and/or
H2S if the pressure is below 500 psia. Above 500 psia, acid gases must be accounted for by rigorous three-phase flash cal-
culations [11] or approximation methods [12].

Hydrocarbons in Water
An easy to use nomograph has been developed for the solubility of liquid hydrocarbons in water at ambient conditions
(25°C). The accuracy of the nomograph has been checked against available solubility data. Performance of the nomograph
has been compared with the predictions given by two available analytical correlations. The nomograph is much simpler to
use and far more accurate than either of the analytical methods.
Two main sources of data were used to develop the nomograph: McAuliffe [13] and Price [14]. The hydrocarbons were
divided into 14 homologous series as listed in Table 29.9. Solubilities at 25°C were then regressed with the carbon numbers
of the hydrocarbons to obtain the best fit for each homologous series. A second-order polynomial equation fits the data
very well:
 log S ¼ a + bC2 (29.9)
where
S ¼ solubility, mole fraction
a, b ¼ regression constants
C ¼ carbon number of the hydrocarbon
The constants a and b for the different homologous series are given in Table 29.9. The nomograph shown in Fig. 29.2 was
then built with the help of equations for the 14 homologous series. The X and Y coordinates for the different homologous
series are listed in Table 29.9. The carbon number range of the nomograph is 4–10 while the mole fraction range is 109 to
104. Its accuracy beyond these ranges is not known.
As an example of the use of the nomograph, the line is shown which would be drawn to determine the solubility of
n-hexane in water at 25°C. The coordinates given in Table 29.9 for normal paraffins have been used: X ¼ 15.0,
Y ¼ 20.0. The predicted solubility is 2  106 mole fraction; the experimental value is 1.98  106 as given by McAuliffe
[13] and Price [14].
 Properties Chapter 29 473

TABLE 29.8 Bulk Modulus

Fluid Temperature °C SI Units (109 Pa) US Units (105 lbf/in2) Source

Acetic acid 20 1.10 1.60 5
Acetone 20 0.78 1.13 5
Aniline 20 2.21 3.21 5
Benzene 20 1.07 1.55 5
Benzene, chloro- 20 1.34 1.94 5

n-Butyl alcohol 0 1.23 1.78 5

Carbon disulfide 20 1.08 1.57 5
Carbon tetrachloride 20 0.97 1.41 5
Chloroform 20 1.01 1.46 5
Cyclohexane 25 0.90 1.31 5
Dodecane 60 0.88 1.28 5

Ethyl alcohol 20 0.89 1.29 5

Ethyl bromide 20 0.77 1.12 5
Ethylene chloride 20 1.25 1.81 5
Ethyl ether 20 0.54 0.78 5
Gasoline Not specified 1.3 1.9 7
Glycol 25 2.69 3.90 5

n-Heptane 25 0.70 1.02 5

1-Heptanol 0 1.42 2.06 5
n-Hexane 25 0.62 0.90 5
1-Hexanol 0 1.34 1.94 5
Mercury 20 25.00 36.26 5
Methyl alcohol 20 0.83 1.20 5

Methylene bromide 16.9 1.55 2.25 5

Methyl iodide 16.9 1.03 1.49 5
n-Octane 25 0.83 1.20 5
1-Octanol 0 1.47 2.13 5
Paraffin oil Not specified 1.66 2.41 7
n-Pentadecane 60 0.98 1.42 5

Petrol Not specified 1.07–1.49 1.55–2.16 7

Phenol 60 1.65 2.39 5
n-Propyl alcohol 0 1.19 1.73 5
SAE 30 oil Not specified 1.5 2.2 7
Toluene 20 1.12 1.62 5
Water 20 2.18 3.16 5

Seawater Not specified 2.34 3.39 7

m-Xylene 20 1.18 1.71 5
FIG. 29.1 Water content of lean, sweet natural gas [11].

TABLE 29.9 Regression Constants and Nomograph Coordinates for the Solubilities of Liquid Hydrocarbons in Water at 25°C

Regression Nomograph
Constants Coordinates

Homologous Series No. of Compounds a b X Y

Normal paraffins 7 3.81 0.0511 15.0 20.0
Isoparaffins—monosubstituted 8 3.91 0.0476 18.0 21.5

Isoparaffins—disubstituted 7 4.02 0.0409 23.2 25.1

Isoparaffins—trisubstituted 3 5.23 0.0186 47.1 20.8
Naphthenes—nonsubstituted 4 3.45 0.0378 26.0 40.0
Naphthenes—monosubstituted 4 3.48 0.0441 20.7 33.1
Naphthenes—di- and trisubstituted 4 4.75 0.0228 41.8 27.2
Alkenes—normal and monosubstituted 10 3.25 0.0479 18.0 34.0

Dienes 5 2.79 0.0460 19.1 43.9

Cycloalkenes 4 2.69 0.0460 19.1 46.1
Acetylenes 6 2.32 0.0469 18.9 52.5
Diynes 2 1.51 0.0391 25.0 76.8
Aromatics—single ring, mono- and disubstituted by n-paraffins 6 1.91 0.0418 23.5 66.1
Aromatics—single ring, monosubstituted by isoparaffins 2 2.99 0.0264 37.5 62.6
 Properties Chapter 29 475

FIG. 29.2 Nomograph for the solubility of liquid hydrocarbons in water at 25°C.

Methanol Injection
Methanol is frequently used to inhibit hydrate formation in natural gas so we have included information on the effects of
methanol on liquid phase equilibria. Shariat, Moshfeghian, and Erbar [15] have used a relatively new equation of state and
extensive calculations to produce interesting results on the effect of methanol. Their starting assumptions are the gas
composition in Table 29.10, the pipeline pressure/temperature profile in Table 29.11, and methanol concentrations
sufficient to produce a 24°F hydrate-formation-temperature depression. Resulting phase concentrations are shown in
Tables 29.12–29.14. Methanol effects on CO2 and hydrocarbon solubility in liquid water are shown in Figs. 29.3 and
29.4. Sources for this section are Refs. [8,15,16].
Here are some conclusions from the study:
1. Water or water plus methanol has negligible effect on predicted liquid hydrocarbon knockout.
2. Methanol causes substantial enhancement of CO2 solubility in the water phase (Fig. 29.3). Watch for increased
corrosion.
3. Methanol concentration has essentially no effect on predicted water content of the liquid hydrocarbon phase. The water
content (not shown in the tables) was about 0.02 mol%.
476 Rules of Thumb for Chemical Engineers

TABLE 29.10 Gas Composition

Component Mol%
N2 2.85
C1 79.33
CO2 5.46
C2 4.19
C3 2.00

iC4 0.44
nC4 0.78
iC5 0.40
nC5 0.34
Lt. arom. 0.34
C6* 3.87

Total 100.00

TABLE 29.11 Pipeline Pressure Temperature Profile*

P (psia) T (°F)
2000** 150**

1800 100
1600 80
1400 70
1200 60
1000*** 60***
*
Primary separator operates at 150°F and 2000 psi.
**
Inlet from separator.
***
Discharge from pipeline.

TABLE 29.12 Results Based on Dry Hydrocarbon Flash

Water (lb/MMscf) Methanol
Pressure/Temperature Hydrocarbons Vapor Phase
(psia/°F) (bbl/MMscf) Liquid Vapor Water-Rich Liquid (wt%) (Lb/MMscf)
2000/150 0 – 131.0 – 86.1
1800/100 3.36 95.0 36.0 – –
1600/80 4.57 107.0 24.0 – –
1400/70 5.19 114.5 16.5 – –

1200/60 5.75 118.8 12.2 – –

1000/60 5.59 117.8 13.2 24.75 47.03
 TABLE 29.13 Results Based on Wet Hydrocarbon Flash
Water (lb/MMscf) Methanol
Pressure/Temperature Hydrocarbons Vapor Phase
(psia/°F) (bbl/MMscf) Liquid Vapor Water-Rich Liquid (wt%) (Lb/MMscf)
2000/150 0 0 137.8 – 86.1
1800/100 3.36 94.5 43.3 – –
1600/80 4.56 111.4 26.4 – –

1400/70 5.18 116.9 20.9 – –

1200/60 5.72 121.3 16.5 – –
1000/60 5.58 119.7 18.1 24.75 47.03

TABLE 29.14 Results for Wet Methanol-Hydrocarbon Flashes

Water (lb/MMscf) Methanol

Pressure/Temperature Hydrocarbons Vapor Phase
(psia/°F) (bbl/MMscf) Liquid Vapor Water-Rich Liquid (wt%) (Lb/MMscf)
2000/150 0 0 137.8 – 85.15
1800/100 3.36 98.8 39.0 16.22 64.43
1600/80 4.69 114.9 22.9 20.40 52.07
1400/70 5.33 120.1 17.7 22.68 45.24
1200/60 5.90 124.1 13.7 24.78 38.20
1000/60 5.74 122.8 15.0 24.77 38.56

FIG. 29.3 Effects of methanol on predicted CO2 solubility in water phase.

478 Rules of Thumb for Chemical Engineers

FIG. 29.4 Effects of methanol on predicted hydrocarbon solubility in liquid water.

4. For this problem, methanol had no practical effect on the solubility of hydrocarbons in the water phase (Fig. 29.4).
5. Methanol causes a 10%–15% reduction in the predicted water content of the pipeline gas.

COMPRESSIBILITY FACTOR
For gas-phase calculations, such as pressure drop (Chapter 4) and compressor performance (Chapter 8), the compressibility
factor can be adequately estimated using the Redlich–Kwong equation of state.
RT a
P¼  (29.10)
Vm  b Vm ðVm + bÞT 0:5
where
R2 Tc2:5
a¼
2:3393Pc
RTc
b¼
11:5420Pc

Vm a
Z¼  (29.11)
Vm  b RTðVm + bÞT 0:5
Knowing the pressure, temperature, critical pressure, and critical temperature of the gas, solve Eq. (29.10) for Vm, the
molecular volume. Use Goal Seek in Excel or the Excel VBA subroutine listed below. If pressure is in units atm and tem-
perature in K, the value of R is 0.08206.
 Properties Chapter 29 479

Function ZSI(P, T, Pc, Tc)

’ calculates compressibility factor, Z, using SI units
’ P = gas pressure, kPa
’ T = gas temperature, C
’ Pc = gas pseudo-critical pressure, atm
’ Tc = gas pseudo-critical temperature, C
’ a = Redlich-Kwong parameter with Pc in atm and Tc in K
’ b = Redlich-Kwong parameter with Pc in atm and Tc in K
’ convert P to units atm
P = P * 0.009869233
’ convert T to units K
T = T + 273.15
Tc = Tc + 273.15
R = 0.08206 ’gas constant
’ calculate Redlich-Kwong parameters
a = (R ^2 * Tc ^2.5) / (2.3393 * Pc)
b = R * Tc / (11.542 * Pc)
’ calculate the molecular volume, Vm
VmLow = 0.000001
VmHigh = 100
Vm = (VmLow + VmHigh) / 2
j=0
Do
j=j+1
RHS = R * T / (Vm - b) - a / (Vm * (Vm + b) * T ^0.5)
If RHS < P Then
VmHigh = Vm
Vm = (VmLow + VmHigh) / 2
Else
VmLow = Vm
Vm = (VmLow + VmHigh) / 2
End If
Loop While Abs((RHS - P) / P) > 0.001 And j < 1000
ZSI = Vm / (Vm - b) - a / (R * T * (Vm + b) * T ^0.5)
If j = 1000 Then ZSI = j
End Function

INORGANIC GASES IN PETROLEUM

ASTM provides a standard method for estimating the equilibrium solubility of common inorganic gases in petroleum
liquids. The method applies to petroleum liquids having densities from 0.63 to 0.90 g/mL at 15.5°C (approximately
93° to 25° API at 60°F). The results are given as parts per million by weight for the specified partial pressure of the
gas and for specified temperatures in the range from 45°C to 150°C (50°F to 300°F).
The following short VBA function subroutine calculates the solubility. After entering the code into an Excel Module,
call it from an Excel worksheet with the formula:
¼GasSol(OC, MW, T, D, P, VP)
where
OC ¼ Ostwald coefficient (see Table 29.15)
MW ¼ molecular weight
T ¼ temperature (°C)
D ¼ density (kg/m3)
P ¼ pressure above the liquid surface (atm absolute)
VP ¼ vapor pressure of the liquid (atm absolute)
480 Rules of Thumb for Chemical Engineers

TABLE 29.15 Ostwald Coefficient Vo for 0°C

Gas Ostwald Coefficient

Air 0.095
Ammonia 2.80
Argon 0.23
Carbon dioxide 1.00
Carbon monoxide 0.10

Hydrogen 0.039
Krypton 1.30
Nitrogen 0.075
Oxygen 0.15
Xenon 2.00

Function GasSol(OC, MW, T, D, P, VP)

’Estimates gas solubility in petroleum liquid
’Limited to liquid density between 630 and 900 kg/m3
’
’OC = Ostwald Coefficient at 0C
’MW = gas molecular weight
’T = temperature, degC (default is 0)
’D = density of liquid, kg/m3 (default is 850)
’P = total pressure, atm abs (default is 1)
’VP = vapor pressure of liquid, atm abs (default is 0)
T = T + 273.15
If D = 0 Then D = 850
If P = 0 Then P = 1
’ convert density to g/ml
D = D / 1000
’ correct for temperature
V = 0.3 * Exp(0.639 * ((700 - T) / T) * Log(3.333 * OC))
’ correct for liquid density
If D <> 850 Then V = V * 7.7 * (0.98 - D)
’ correct for pressure
B = 273 * P * V / T
G = (B * MW / 0.0224) * (D * (1 - 0.000595 * ((T - 288.6) / D ^1.21))) ^(-1)
’ correct for vapor pressure
If VP > 0.1 * P Then G = ((P - VP) / P) * G
GasSol = G
End Function

FOAM DENSITY
Zanker gives this equation for estimating the density of foam on distillation and absorption column trays [17]. He says it
agrees well with published data.


f
dF ¼ dL 1  0:46 log (29.12)
0:0073
 Properties Chapter 29 481

where
 0:5
dV
f ¼u
ð dL  d V Þ

dF ¼ foam density (lb/ft3)

dL ¼ liquid density (lb/ft3)
dV ¼ vapor density (lb/ft3)
u ¼ superficial vapor velocity (ft/s)

EQUIVALENT DIAMETER
Zanker’s article, reprinted here, gives a way to estimate the elusive equivalent diameter of solids [18]. For further reading,
refer to http://ciks.cbt.nist.gov/garbocz/monograph/3-D_Particles/dimensions.htm.

Estimating Equivalent Diameter of Solids

Particle diameter is a primary variable important to many chemical engineering calculations, including settling, slurry flow,
fluidized beds, packed reactors, and packed distillation towers. Unfortunately, this dimension is usually difficult or impossible
to measure, because the particles are small or irregular. Consequently, chemical engineers have become familiar with the
notion of “equivalent diameter” of a particle, which is the diameter of a sphere that has a volume equal to that of the particle.
The equivalent diameter can be calculated from the dimensions of regular particles, such as cubes, pyramids, cylinders,
cones, and so on. For irregular particles, the equivalent diameter is most conveniently determined from such data as the
fractional free volume and the specific surface or area of the particle in a bed of the particles, as determined experimentally
from measurements that determine particle volume as a displaced fluid.
These two nomographs provide a convenient means of estimating the equivalent diameter of almost any type of particle:
Fig. 29.5 of regular particles from their dimensions, and Fig. 29.6 of irregular particles from fractional free volume, specific
surface, and shape.

Equivalent diameters of regular-shaped bodies 0.02 0.02

5.0
0.02 0.03
4.0 0.03
De = equivalent diameter of spherical body, in.

0.04

pyramids and cones; (0.6 h) for ellipsoids; and (0.7 h) for pellets
3.0 0.03 0.04
0.0005 0.05 0.05
0.04 0.06
2.0 0.001 0.06
0.05
0.002 0.06 0.08 h for parallelepipeds and cylinders; (h/3) for rectangular 0.08
0.003 0.10
0.10
d = diameter of a body, in.

0.005 0.08
1.0
0.10
b = width of a body, in.

0.01
0.8
0.02
0.6 0.03 0.2 0.2
(1)
0.5 0.05
a = length of a body, in.

0.2 0.3
0.4 0.1 0.3
0.3 0.2 0.3 0.4
0.4
Reference line

0.3
0.5 0.5 0.5
0.4
0.2 0.6 0.6
1.0 0.5
2.0 0.6 0.8 (2) 0.8
3.0 1.0
5.0 0.8 1.0
0.1
10 1.0
0.08
20 2.0
0.06 2.0
0.05
2.0 3.0
0.04 3.0
0.03 3.0 4.0 4.0
5.0 5.0
0.02
FIG. 29.5 Equivalent diameters of regular-shaped bodies.
482 Rules of Thumb for Chemical Engineers

Equivalent diameters of
irregular and complicated bodies
0.20 Spherical: 0.30 30 8
Arnould’s wire spirals smooth, mixed
20 10
Spherical: 0.40 15
0.25 smooth, uniform 10 15

e = fractional free volume (voltage), dimensionless

Cylindrical: 0.50
Mica flakes
j = shape factor of the solid, dimensionless

smooth, uniform 6 20

e = equivalent diameter of spherical body, in.

0.30 Berl saddles Granules
Raschig rings 4
0.60
3 30
0.35 (1)

s = specific surface, ft2 per ft3 of bed

Raschig rings, 0.65 2
Fusain fibers 40

Reerence line
clay 1.5
0.40 Flint sand, jagged flakes 0.70
Flue dust, fused, aggregates
Raschig rings, steel 1.0 50
0.45 (2)
60
0.6 70
0.75
0.50 0.4 80
Result
Flint sand, jagged 0.3 100
0.55
Glass, crushed, jagged 0.80 0.2
0.60
Coal dust, average 0.15
150
Cork 0.10
0.70 Sand, angular 0.85 200
Sand, average 0.06
0.80 Sand, rounded
0.04 300
Tungsten powder
0.03
0.90 Flue dust, fused, spherical
Sand, nearly spherical 0.02 400
1.00 Spheres 0.90 500
FIG. 29.6 Equivalent diameters of irregular and complicated bodies.

Also, in cases where the dimensions of a regular particle vary throughout a bed of such particles or are not known, but
where the fractional free volume and specific surface can be measured or calculated, the shape factor can be calculated and
the equivalent diameter of the regular particle determined from Fig. 29.6.
In Fig. 29.5, the equivalent diameter is related to regular shapes through equivalent volumes by the following formulas:
p ffiffiffiffiffiffiffiffiffiffiffi 6ð1  eÞ
De ¼ 3
6V=p¼ (29.13)
’s
where the terms are in consistent units of length
V ¼ volume of shape (see a ¼ length of base edge
b ¼ width of base measured perpendicular to plane a
d ¼ diameter
h ¼ height measured perpendicular to plane ab (see Table 29.16)
e ¼ fractional free volume, dimensionless
’ ¼ shape factor ¼ area of sphere divided by the surface area of a particle of equal volume

TABLE 29.16 Formulas to Determine Volume of Various Shapes

Shape Formula
Parallelepiped V ¼ ab c
Cube V ¼ a3
Rectangular pyramid V ¼ ðab Þh=3
 
Cylinder V ¼ h d 2 p=4
 
Cone V ¼ d 2 p=4 ðh=3Þ
 
Pellet V ffi 0:7h d 2 p=4
 
Ellipsoid V ffi 0:6h d 2 p=4
 Properties Chapter 29 483

FIG. 29.7 Data sheet for summarizing physical properties.

484 Rules of Thumb for Chemical Engineers

s ¼ specific surface ¼ particle surface per unit volume of bed

a ¼ length of base edge
b ¼ width of base measured perpendicular to plane a
d ¼ diameter
h ¼ height measured perpendicular to plane ab

Examples
What is the equivalent diameter of a rectangular pyramid with base sides 1 and 2 in and a height of 1.5 in? In Fig. 29.5, align 1.0 (or
2.0) on the a scale with 2.0 (or 1.0) on the b scale and note the intersection of this line on the reference line. Align this intersection
with h/3 ¼ 0.5 and read De ¼ 1.24 in.
What is the equivalent diameter of a pellet with a diameter of 0.5 in and a length of 0.5 in? In Fig. 29.5, align 0.5 on the d scale
with 0.35 (0.7 h) and read De ¼ 0.51.
What is the equivalent diameter of crushed glass (f ¼ 0.65) with a fractional free volume of 0.55 and a specific surface of 80? In
Fig. 29.6, align f ¼ 0.65 with e ¼ 0.55 and note the intersection on the reference line. Align this with s ¼ 80 and read De ¼ 0.62.

PROPERTIES DATA SHEET

Assemble applicable physical properties in the project’s document management system whether it is paper based or digital.
A data sheet makes a convenient tool for capturing basic data, ensuring that team members use the same information, and
helping to identify missing values. The Excel workbook for this chapter includes a blank data sheet (Fig. 29.7).

REFERENCES
[1] C. Branan, The Process Engineer’s Pocket Handbook, Vol. 3, Gulf Publishing Co, Houston, Texas, 1976.
[2] R.H. Perry, D.W. Green, in: Perry’s Chemical Engineers’ Handbook, sixth ed., McGraw-Hill, New York, 1984.
[3] A. Zanker, Find emulsion viscosity through use of nomograph, Hydrocarb. Process., January, 1969, p. 178.
[4] ASTM Standard D88-07, Standard Test Method for Saybolt Viscosity, ASTM International, West Conshohocken, PA, 2007, DOI: 10.1520/D0088-07.
Available from: https://www.astm.org.
[5] ASTM Standard D2161-05e1, Standard Practice for Conversion of Kinematic Viscosity to Saybolt Universal Viscosity or Saybolt Furol Viscosity,
ASTM International, West Conshohocken, PA, 2005, DOI: 10.1520/D2161-05.
[6] P.H. Pallady, Compute relative humidity quickly, Chem. Eng., November, 1989, p. 255.
[7] R.H. Perry, D.W. Green, in: Perry’s Chemical Engineers’ Handbook, fifth ed., McGraw-Hill, New York, 1973.
[8] GPA Midstream Association, GPSA Engineering Data Book, SI Version, vol. 2, fourteenth ed., 2017.
[9] B. Spang, Excel Add-In for Properties of Water and Steam in SI Units, Available from: http://www.cheresources.com/staff.shtml.
[10] P.C. Singh, S. Singh, Development of a new correlation for binary gas dispersion coefficients, Int. Commun. Heat Mass Transfer 10 (1983) 123–140,
http://dx.doi.org/10.1016/0735-1933(83)90039-8.
[11] V. Kabadi, R. Danner, Nomograph solves for solubilities of hydrocarbons in water, Hydrocarb. Process., May, 1979, p. 245.
[12] A. Fredenslund, R. Jones, J. Prausnitz, Group-contribution estimation of activity coefficients in non-ideal liquid mixtures, AIChE J. 21 (1975)
1086–1099.
[13] C.J. McAuliffe, J. Phys. Chem. 70 (1966) 1267–1275.
[14] L. Price, American association of petroleum geologists, Bull. 60 (1976) 213.
[15] A. Shariat, M. Moshfeghian, J. Erbar, Predicting water knockout in gas lines, Oil Gas J., November 19, 1979, p. 126.
[16] J. Erbar, R. Maddox, Water-hydrocarbon system behavior, Oil Gas J., March 16, 1981, p. 75.
[17] A. Zanker, Quick calculation for foam densities, Chem. Eng., February 17, 1975.
[18] A. Zanker, Estimating equivalent diameters of solids, Chem. Eng., July 5, 1976, p. 101.

FURTHER READING
ASTM Standard D2779-92(2007), Standard Test Method for Estimation of Solubility of Gases in Petroleum Liquids, ASTM International, West Con-
shohocken, PA, 2007, DOI: 10.1520/D2779-92R07. Available from: https://www.astm.org.
Chemical Rubber Co., Handbook of Chemistry and Physics, fiftieth ed., 1969.
The Engineering Toolbox, Bulk Modulus Elasticity, Available from: http://www.engineeringtoolbox.com (Accessed September 2010).
A. Fredenslund, J. Gmehling, P. Rasmussen, Vapor-Liquid Equilibria Using UNIFAC: A Group Contribution Method, Elsevier Scientific Pub. Co,
Amsterdam, Oxford, New York, 1977.
The International Association for the Properties of Water and Steam (IAPWS), Revised Release on the IAPWS Formulation 1995 for the Thermodynamic
Properties of Ordinary Water Substance for General and Scientific Use, Doorwerth, The Netherlands, 2009. Available from: http://www.iapws.org.