Estimation of Physical Properties

Data collection, selection and

processing
 Sources of Data
• Process Design is one of chemical engineering’s
exciting careers.
• This career deals with a lot of data and information
processing.
• Data and information processing tools and sources are
core to process design.
• Data and information can be found from various data
and information `banks`.
• These can be found as soft materials from engines, e.g.
Google, data bases, process simulation packages such
Aspen Plus and hard copies from libraries e.g. Perry’s
Handbook, Encyclopaedia of chemical technology,
Ullman’s Encyclopaedia of industrial technology, CRCs
handbook etc
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 Sources of Data
• Care should be taken when choosing the source
to collect data.
• The quoted sources above are most used by
Chemical Engineers.
• However, some consulting firms can provide
valuable data and information for process design.
• Depending of the company that you will work for
some companies have access to process data that
can be used for process re-engineering.

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 Sources of Data
• International Critical tables contained invaluable
data for physical properties of substances and
are also found in most libraries.
• Elsevier or www.science direct is a credible
website a to visit for data and information series
and it has series of volumes on physical
properties of substances.
• www.engineeringToolBox is also a good website
for data and information collection

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 Data accuracy of engineering data
• In preliminary design Data accuracy is not important.
• In final design stage very accurate data is required.
• High accuracy must be considered for sensitive
design parameters.
• If a small error in the parameter will cause a major
effect on the design, then high accuracy data needs
to be considered.
• Physical properties that are found in
handbooks, Encyclopaedia, etc were
determined experimentally with highest
accuracy.
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 Estimation of Physical Properties
• In this chapter some methods of the estimating physical
properties will be done.
• Correlation, extrapolation and interpolation of
experimentation data in cases were the process design
condition fall outside the available data.
• Common Physical properties used in design are:
– Density
– Viscosity
– Thermal Conductivity
– Specific Heat Capacity
– Enthalpy of Vaporization.
– Vapour Pressure
– Diffusion Coefficients.
– Surface Tension
– Enthalpy or Reaction and Enthalpy of Formation
– etc

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 Estimation of Density
• Density is a physical property
• Units : kg/m3
• Density is also an intensive property meaning it does
not depend on the mass of the substance.
• However, is Temperature dependent.
• E.g. We always use 1000kg/m3 as a reference for the
density of water without specifying the temperature.
• It is imperative that, we always specify the
temperature when quoting density data.

1000kg / m3 @ 4 o C
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 Estimation of Density
• Densities of pure compounds (gases, liquids and solids
are given in Perry’s handbook.
• Sometimes density is presented as specific gravity, S.G.
• Specific gravity, S.G. is the density of a substance
relative to the density of a certain reference substance
at a reference temperature.
• The reference substance for most non-volatile liquids is
usually water at 4oC (i.e. 1000 kg/m3).

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 Estimation of Density
• Physical properties of substances are limited only to
pure substances.
• The data for mixtures is not readily available.
• Mixture are combined in certain ratios e.g. mole
fractions or mass fractions.
• Density of a single component (i) in solution is:
• Density of a solution(sln) is:
• Where is sum of density of various comp.:

• Sum density of a sln therefore is:

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 Estimation of Density
It is easier to express as mass fraction wi.
Vi mi
  wi and n   wi  i n
V mn
Density can be expressed in terms molar volumes at boiling
points as done by see Sinnott 1999:333 (Coulson and
Richardson vol 6) table 8.6
V
Molar volume is volume per moles of a substance: m n V 

Because of moles, now the density is expressed in terms

M
of molar mass (M):   V
m
Relative molecular weight of a solution is:
and

Which is made of various components (i) that make up

a solution: M   MW  w 
i i n 10
 Estimation of Density
Task 1:
The densities of water and methanol at 20oC are 998.2
and 791.2 kg/m3, respectively. Calculate the density of
the mixture at 40%w/w of methanol.

This is how we going to solve problem in this class

 Do it alone first (5min).
 Turn to the neighbour to confirm solution (2.0min).
 Consolidate, correct. (2.0min).
 Raise hand your hands (for tutor’s attention)

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 Worked Example
Because of the %by weight(w/w) we make basis for the
total solution:
What basis?
A)Volume
B)Mole
C)Mass
C) Mass basis because of % by weight
What quantity of the solution is assume as basis?
A) 100 g
B) 100 kg  because density in kg/m3
C) 1000 kg  because density in kg/m3
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 Worked Example
• Basis:1000 kg solution of methanol + water
• We have got mass of the solution (1000 kg), need to
calculate volume.
 wi  Vi
• Definition or
    
 i  mn
0.4 1000kg
Vmeth   0.506 m3 0.4 1000kg
791.2kg / m 3
and Vwater  3
 0.601 m3
998.2kg / m
Total volume is : Vm = Vmeth + Vwater
Vm = 0.506m3 + 0.601m3 = 1.107 m3
m( s ln) 1000kg
  3
 903.3kg / m3 As in Sinnott 1999:314
V ( s ln) 1.107m

Experimental value = 934.5 kg.m-3 Sinnott 1999:314

The class calculated = 915.5 kg.m-3

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 Estimation of Vapour and Gas Density
At moderate pressures Ideal Gas behaviour:
m PM
PV  nRT PV 
M
RT PM 
m
RT PM  RT 
RT
V
Other useful property is V
 RT Vˆ 
RT
specific molar volume V: Vˆ P
n P

For accurate estimation moderate pressures Real gas

behaviour:
PV  znRT
z - Compressibility factor
- values can be found in Sinnott 1999:87 (Coulson and
Richardson vol 6) using compressibility chart (slide 15)

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 Density of Gas Mixtures
• For gas mixtures the pseudo-critical properties of the
mixtures should be used to obtain the compressibility factor,
z.

Where:
Pc = critical pressure,
Tc. = critical temperature,
y = mol fraction,
Suffixes:
m = mixture
a, b, c etc. = components

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Real Gas Behaviour –
Compressibility Chart

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 Compressibility Chart –
Useful Info & Equations
• Reduced Temperature, Tr :

• Reduced Pressure, Pr :

• Where Tc and Pc are the Critical Temperature and Pressure

respectively.
• Tc – the Temperature at and above which vapour or gas of a
substance can no longer be liquefied, regardless of the amount of
pressure applied
• Pc – the Pressure at which the critical temperature occurs
• T and P – the Temperature and Pressure of the system in question
• Tc and Pc can be obtained from the Physical Data Bank in C&R
• Z = 1 is indicative of an ideal gas
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 Estimation of Viscosity
Modified Arrhenius equation: mb  0.01b0.5
• mb  viscosity (mNs/m2).
• b = density at boiling point. A good estimate at
boiling points
Souder’s equation is more accurate :
I
• m  viscosity (mNs/m ). m  3
2 log(log 10 )   10  2.9
M
•  = density at required temperature.
• M = molar mass
• Souders index (I) can be estimated from the
contributions (see table 8.1, Sinnott:316)

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Souder’s Index:

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 Estimation of Viscosity
Task 2:
Estimate the viscosity of Toluene at 20oC using
Souder’s equation,
Given: Density of Toluene at 20 oC = 866 kg/m3

Do it alone first (5min). Hints

Turn to the neighbour to confirm (2.0min). Structure of toluene
Consolidate, correct. (2.0min). Use table 8.1 (Sinnott 1999:31).
Raise your hand (for tutor’s attention) Use contributions to determine I
Pay careful attention to units

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 Estimation of Viscosity
• Viscosity can be estimated from curves e.g. Figure
8.1 (Sinnott:317, as slide OHP slide)
• 20% accurate.
• Viscosity is affected at high
pressures (300bars)

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 Estimation of Viscosity from Curves:
Task 3:
Use the value of viscosity calculated in the previous activity to
estimate the viscosity of toluene at 80oC.

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 Estimation of Viscosity of Mixtures
• Viscosity are not additive like densities.
• Viscosities of mixture can be lower or higher than
pure substances that combine to make a mixture.
• A modified Souder’s equation is used for organic
liquids.  x1I1  x2 I 2 
log(log 10mm)    103  2.9


m
– Uses mole fractions (xi).  1 1 2 2
x M x M

– Weighted average of the viscosities (mm) for the mixture

index (Im ).
– Molecular masses of components (Mi).
– Density of the mixture (m).

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 Estimation of Viscosity of Mixtures in
heat transfer calculations
• Viscosity of Mixtures in heat transfer
environment can be calculated from:
1 w1 w2
 
mm m1 m2

• mass fraction (wi) of components 1, 2, 3…

• viscosities of components (mi)of components
1, 2, 3,…

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 Estimation of Viscosity
• 3 Methods for pure components:
– Arrhenius, Souder and Graphic
• 2 Methods for mixtures:
– Souder – including mass fractions, and
– Kern – for heat transfer
• Units are in mNs/m2 = mPa.s = cP
– 1 cP = 0.001 Pa.s or 1 Pa.s = 1000 cP
• To help solve Souder’s Equation use LOG law:
–

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Practice Problems –C&R Vol. 6

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 Thermal Conductivity
• Thermal conductivity for solids is found in many Physics
textbooks.
• Thermal conductivity (k) for organic liquids can be estimated
from density (ρ), molecular mass (M), and specific heat
capacity (Cp) by using Weber Equation in heat transfer
calculations 1
  4

3

k  3.56 10 C p  
5

M 

Task 4: prove that the unit of k  W/moC, that are in the

Weber Equation?
Density ()  kg/m3
Molecular mass (M)  kg/kmol?
Specific heat capacity (Cp)  kJ/kgoC
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 Thermal Conductivity
Task 5:
Estimate the thermal conductivity of benzene at
30oC.
ρbenz@30oC = 875 kg.m-3
(Cp) = 1.75 kJ/kgoC
M = 78
Substitute into the equation?
Answer = 0.12 W/moC
Experimental value = 0.16 W/moC

1
 875
4

3

k  3.56 10 1.75  

5
  0.12W / moC
 78 

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 Thermal Conductivity of Gases
At moderate pressure, thermal conductivity of gases
can be estimated by Eucken’s Equation:
 10.4 
k  m Cp  
Task 6:  M 
Estimate the thermal conductivity of ethane at one
bar and 450oC. The viscosity is 0.0134mNs/m2 and
Cp = 2.47kJ/kgoC. (Experimental value is 0.043W/moC )

 10.4   10.4 
k  m Cp   k  0.0134 2.47    0.038W / m C
o

 M   30 

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 Thermal Conductivity of Mixtures
For non-polar components, the thermal
conductivity of the mixture can be calculated
from the components thermal conductivity
(ki) and mass fractions (wi).
k = kiwi
k = k1w1+k2w2 +…

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 Specific Heat Capacity
Cp of Liquid & Solids
The Heat Capacity of a compound is the sum of the
heat capacities of individual elements that make up the
compound. Heat Capacities of the elements are given
in the units J/moloC .
The units of Cp are given in kJ/kgoC  J/goC
Cp 
 Cp i

M
Task 7:
Estimate the specific heat capacity of urea,
CH4N2O, from elemental heat capacities data.
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 Estimation of Heat Capacities
from elements
• This table give
heat capacities
elements that
make up many
substances.
• However it does
not take into
accounts the
arrangements of
Hence, this data can only be atoms, and
used in the preliminary therefore is not
designs. very accurate.
This table applies to solids and
liquids only
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 Element No. Cp’s From Elem. X Cps
Task 7 Solution: elements Cp table

 Cpi
C 1 7.5 7.5
Cp  H 4 9.6 38.4
M
N 2 26.0 52
M= 60kg/kmol O 1 16.7 16.7
114.6 J / mol oC Cpi 114.6 J/moloC
Cp   1.91kJ / kg oC
60kg / mol

Experimental value =1.34kJ/kgoC

The Specific Heat Capacity can be estimated with better
accuracy by using Chueh and Swanson Method – Group
Contribution Method (See tables).

This table applies to solids and liquids only

This method considers the structure of the compounds 33

Chueh and Swanson
Method

 Chueh and Swanson

table comes with
some additional rules.
 Needs knowledge of
the structural formula.
 Students are required
to revise Organic
Chemistry I &II

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 Heat Capacities of Liquid & Solids
Chueh and Swanson Method uses group contribution
values. Each structure of the compound is regarded as
the group and the value associated with the group is
called a contribution.
Group contribution values are additive.

Task 8:
Use Chueh and Swanson Method to estimate the
specific heat capacity of ethyl bromide, CH3CH2Br.
(Experimental Value = 0.90 kJ/kgoC)

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 Heat Capacities Liquid & Solids
Use Chueh and Swanson Method to estimate the
specific heat capacity of ethyl bromide at 20oC.
Group No. of Groups Contri. values X No. of Cps
Groups

-CH3 1 36.84 x 1
36.84
-CH2- 1 30.40 x 1
30.40
-Br 1 37.68 x 1 37.68
Contributions= 104.92 kJ/moloC

Cp 
 Cp i
Cp 
104.92
 0.96kJ / kg oC
M 109
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 Specific Heat Capacity of Gases
At constant pressures, heat capacities of gas
mixtures can be estimated from :
Cp = a + bT + cT2 + dT3

Group Contribution from Rihani and Doraiswamy

(1965) for organic compounds can also be used .
Task 9:
Estimate the specific heat capacity of isopropyl
alcohol at 500 K.

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38
39
40
41
Task 10 Solution:
Estimate the specific heat capacity of isopropyl alcohol at 500 K.

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Enthalpy of Vaporization (Latent Heat)
Trouton’s rule (Trouton, 1884) is used to estimate
latent heat.:

Where:

For organic liquids the constant can be taken as 100

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Enthalpy of Vaporization (Latent Heat)
It can also be estimated from Haggenmacher equation:

44
 Enthalpy of Vaporization (Latent Heat)
At known boiling points, Watson’s equation can be used:

Over a limited range of temperature, up to 100 ̊C, the

variation of latent heat with temperature can usually be taken
to be linear
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Enthalpy of Vaporization (Latent Heat)
Antoine Equation:

Where:
P = Vapour pressure, mmHg
A, B, C = Antoine coefficients
T = Temperature, K.
(1 bar = 750.06 mmHg)

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 Enthalpy of Vaporization for Mixtures
Lv for Mixtures are additive

Task 11:
Estimate the latent heat of vaporization of acetic
anhydride, C4H6O3, at its boiling point, 139.6 oC (412.7 K),
and at 200oC (473 K).
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 Critical Constants
• Lydersen Method – contribution method

where Tc = critical temperature, K,

Pc = critical pressure, atm (1.0133 bar),
Vc = molar volume at the critical conditions, m3/kmol,
Tb = normal boiling point, K,
M = relative molecular mass,
ΔT = critical temperature increments, Table 8.8,
ΔP = critical pressure increments, Table 8.8,
ΔFV= molar volume increments, Table 8.8.
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