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CONTENTS

1.1 Law of corresponding states ................................................................................................ 2

1.2 Group contribution methods................................................................................................. 2

1.3 (Semi) Empirical correlations ............................................................................................... 3

2 Pure component constants ........................................................................................................... 3

2.1 Critical constants (pressure, temperature, volume, compressibility) ................................... 3

Critical temperature ..................................................................................................... 4

Critical pressure .......................................................................................................... 5

Critical volume............................................................................................................. 6

Critical properties of mixtures...................................................................................... 7

2.2 Normal boiling point ............................................................................................................. 7

2.3 Acentric factor ...................................................................................................................... 8

3 Vapour pressure of liquids ............................................................................................................ 9

4 Thermal properties...................................................................................................................... 14

4.1 Heat capacity / enthalpy..................................................................................................... 14

Vapour heat capacity at constant pressure............................................................... 15

Liquid heat capacity at constant pressure................................................................. 16

Heat capacity of mixtures .......................................................................................... 17

4.2 Enthalpy of phase changes................................................................................................ 18

Enthalpy (heat) of vapourisation (liquid to vapour) ................................................... 18

Enthalpy (heat) of fusion (liquid to solid) ................................................................... 20

4.3 Enthalpy (heat) of formation............................................................................................... 20

5 Physical properties ..................................................................................................................... 21

6 Web sources............................................................................................................................... 21

7 Nomenclature ............................................................................................................................. 22

8 References ................................................................................................................................. 23

9 Appendices ................................................................................................................................. 24

9.1 Group contribution parameters for the Lydersens method ............................................... 24

9.2 Group contribution parameters for the Constantinou and Ganis method ......................... 25

9.3 Group increments for the Fedors method ......................................................................... 27

9.4 Constants for the Antoine equation ................................................................................... 27

9.5 Parameters for method of Harrison and Seaton ................................................................ 28

9.6 Group contribution parameters for Rihani and Doraiswamys method .............................. 29

9.7 Group contribution parameters for Shaws method ........................................................... 31

9.8 Group contribution parameters for Rika and Domalskis method ................................ 32

Many engineering applications require the use of physical properties. Some of these properties are

published in the literature yet in many cases these properties have not been measured yet. Although it

may be possible to measure the physical properties of a substance experimentally, these types of

experiments are often tedious and time consuming. Thus in the absence of reliable experimental data

physical properties need to be estimated with sufficient accuracy for the purpose required. The

purpose of this text is not to discuss all property estimation methods in detail but rather to introduce

some of the common methods used to estimate some properties, specifically the properties used in

chemical thermodynamics.

Various methods are used in development of the estimation correlations. Some are based on theory

with empirical parameters, other totally based on fitting available data while some are based on the

theory of corresponding states. Before we discuss the methods to predict some properties, a short

discussion on some general methods widely used is presented:

Proposed by van der Waals in 1873, the law of corresponding states expresses the generalisation that

equilibrium properties which depend on intermolecular forces are related to the critical properties in a

universal kind of way. The law of corresponding states provides the single most important basis for the

development of correlations and estimation methods. The macroscopic version of the law of

corresponding states is as follows:

All fluids at the same reduced temperature and reduced pressure have the same compressibility

factor.

Consider, for example, a plot of the reduced pressure versus the reduced volume for methane and

nitrogen at saturated conditions and at a reduced temperature of 1.1. (See Figure 1). As seen, the

plots coincide well and illustrate the principle of corresponding states.

10

Reduced Pressure

1 Methane Saturated

Nitrogen Saturated

Methane Tr = 1.1

0.01

0.1 1 10 100 1000

Reduced Volume

The concept of the law of corresponding states is used in the development of compressibility charts

and is the basis for many equations of state. Compressibility charts have been discussed in detail in

Chemical Engineering 254 already and although not being discussed in this course, it should be noted

that compressibility charts are a useful tool in describing PvT behaviour. Successful application of the

principle of corresponding states to PvT data has encouraged similar correlations for other properties

and a number of correlations given here will be based on the law of corresponding states.

Group contribution methods of estimating chemical properties originate from the concept that each

chemical group in a compound contributes to the property in its own unique way. Although not without

flaws, these methods are able to predict some properties with reasonable accuracy. State of the art

group contribution methods, although quite complex, are accurate and reliable enough for most

engineering applications. A number of the simpler group contribution methods for the properties

discussed will be illustrated here.

A number of properties of compounds are fitted to (semi) empirical correlations. Sometimes these

correlations have a theoretical basis with fitted constants (semi-empirical correlations) and sometimes

the correlations are based on the best fit of a mathematical equation with little or no theoretical

foundation (empirical correlations). Care should be taken when applying such correlations: The range

of application is usually given as well as the units. When applied outside the range of application,

incorrect / inaccurate results may be obtained. However, within the range of application, (semi)

empirical correlations often provide a good method for estimating the properties of an equation.

With regard to critical constants, a number of terms need to be defined as they are used extensively in

predicting properties of substances.

Critical point: The critical point is the point (pressure, temperature, specific volume and

compressibility) on the vapour pressure curve at which two co-existing

phases become identical. This point is unique for every pure component.

Critical temperature(Tc): The critical temperature is the temperature at the critical point. This is the

temperature above which a gas can not be condensed by increasing the

temperature, i.e. the temperature above which the liquid phase can not

be formed irrespective of the pressure of the system. The critical

temperature is important in determining the phase boundaries of

compounds and is often a parameter in, amongst others, equations of

state and in vapour pressure correlations.

Reduced temperature (Tr): The reduced temperature is the dimensionless ratio of the temperature to

the critical temperature (both in absolute values), i.e. Tr = T / Tc.

Critical pressure (Pc): The critical pressure is the pressure at the critical point. This is the

pressure above which a gas can not be condensed by decreasing the

temperature. As is the case for the critical temperature, the critical

pressure is often used as parameter in equations of state and in vapour

pressure correlations.

Reduced pressure (Pr): The reduced pressure is the dimensionless ratio of the absolute pressure

to the critical pressure, i.e. Pr = P / Pc.

Critical volume (vc): The critical volume is the specific volume at the critical point, i.e. the

volume occupied by the compound at the critical temperature and

pressure. The critical volume is sometimes used in equations of state as

well as in estimating the volumetric fractions.

Critical compressibility (Zc) The critical compressibility is the compressibility at the critical point

calculated from the critical temperature, pressure and volume. The value

is useful and often used in equations of state. (For methods estimating

the critical compressibility please consult general references).

There are a number of literature sources for the critical constants. Some of them include (On reserve

in the library):

th

Perrys Chemical Engineers Handbook, 7 Edition Chapter 2

th

Properties of Gases and Liquids 4 Edition, Appendix A

CRC Handbook of Physics and Chemistry, Chapter 6

Many chemical thermodynamics textbooks, including the one prescribed for this course, also list some

critical parameters.

Critical temperature

The critical temperature is usually estimated using the normal boiling temperature. Generally the ratio

between the critical temperature and normal boiling temperature is between 1.5 and 1.8. Guldbergs

rule states:

Guldberg

Tc = 1.5 Tb (1)

Tb = 434.3 K

Therefore Tc = 1.5 * 434.3 K = 651 K

The published experimental value is 625 K (Reid and Prausnitz).

The error is thus 4 %.

Prudhomm found that the sum of the normal melting temperature and normal boiling temperature is

approximately equal to the critical temperature and proposed the following rule:

Prudhomm

Tc = Tb + Tm (2)

Example: Estimate the critical temperature of water and ammonia using Prudhomms Rule:

Water:

Tb = 373.15 K, Tm = 273.15 K

Tc = 373.15 + 273.15 = 646.3 K

The published experimental value is 647.3 K (Koretsky).

The error is thus less than 0.2 %.

Ammonia:

Tb = 239.8 K, Tm = 195.4 K

Tc = 239.8 + 195.4 = 435.2 K

The published experimental value is 405.5 K (Reid and Prausnitz).

The error is therefore greater than 7 %.

The above methods are rough and, as seen, are often not accurate enough. More accurate additive or

group contribution methods can be used. One such method is that of Lydersen. This method of

estimating the critical temperature of hydrocarbon and non-hydrocarbon organic compounds uses a

combination of the normal boiling temperature and the molecular structure to estimate the critical

temperature:

Lydersen

Tb

Tc = (3)

0.567 +

T ( T )2

T is the contribution of each functional group to the critical temperature. The values of T for each

group is given in Table 1 in section 9.1

Example: Estimate the critical temperature of cyclohexanol using Lydersens method

OH

Tb = 434.3 K

T = 5 * (-CH2- cyclic) + ( C /\ cyclic) + (-OH alcohol)

= 5 * 0.013 + 0.012 + 0.082

= 0.159

From equation 3:

434 .3

Tc =

[

0.567 + 0.159 .0159 2 ]

= 620K

The error in the value is thus 1 %

Constantinou and Gani proposed a group contribution method that takes into account both the

structural groups (first order) as well as structural isomerisation (second order). As the second order

contributions are quite complicated, only the first order contributions will be discussed here (For more

accurate predictions, the second order contributions can be considered consult the original article

[1]). The critical temperature can be calculated as follows:

Tc

181 .128

(

= ln nTci ) (4)

Where n is the number of functional groups (i) present and Tci the contribution of group (i) present. The

values of Tci are given in Table 2 in section 9.2.

Example: Estimate the critical temperature of cyclohexane using the method of Constantiou and Gani

There is 1 C /\ group, i.e. 4.0330

There is 1 OH group, i.e. 9.7292

Therefore the right hand side of equation 4 is 31.2222.

Solving Tc, the critical temperature is 623 K.

The error less than 0.5 %.

Critical pressure

The critical pressure of organics can be estimated according to the method of Lydersen:

Lydersen:

101325MW

Pc = (Pa ) (5)

(0.34 + p )2

p it the contribution of the functional group to the critical pressure and MW is the molar weight in

g/mol. The values of p for each group is given in Table 1 in section 9.1.

Example: Estimate the critical pressure of fluorotrichloromethane according to the method of Lydersen

M = 137.38 g/mol

P = (Fluoro) + 3 * (Chloro) + (Quatro subst. Carbon)

= 0.224 + 3 * 0.320 + 0.210 = 1.394

From equation 5:

101325 137 .38

Pc = = 4.63 MPa

(0.34 + 1.394 )2

The published experimental value is 4.41 MPa (Reid and Prausnitz).

The error is thus 5 %

Constantinou and Gani proposed a method to estimate the critical pressure, similar to their method of

estimating the critical temperature:

1

0.100220 = n Pci (bar ) (6)

Pc 1.3075

Pci is the contribution of the functional group (i) to the critical pressure and n is the number of groups

(i) present. The values of Pci are given in Table 2 in section 9.2.

Example: Estimate the critical pressure of n-butanol according to the method of Constantinou and

Gani

There are 3 CH2 groups, i.e. 3 * 0.010558

There is 1 CH3 group, i.e. 0.019904

The right hand side of equation 6 is 0.056726.

Solving for Pc the critical pressure is 41.9 bar.

The published value is 44.2 bar (Reid and Prausnitz).

The error is thus 5 %.

The method of Constantinou and Gani, as used, only takes first order interactions into account.

Greater accuracy can be obtained if second order interactions are taken into account, yet, as

previously mentioned, this is beyond the scope of this course.

Critical volume

Methods to calculate the critical volume are similar to those calculating the critical pressure and

temperature. Fedors proposed a method for pure organic compounds:

Fedors

m3

v c = 0.0266 + v

kmol

(7)

v is the contribution of the functional group to the critical volume. The values if v is given in Table 4

in section 9.1

Example: Estimate the critical volume of 2-butanol according to the method of Fedors

v = 4 * (carbon atom) + 10 * (hydrogen atom) + (oxygen atom)

= 4 * 0.034426 + 10 * 0.009172 + 0.018000

= 0.2474

3

vc = 0.0266 + 0.2474 = 0.2740 m /mol.

3

The published experimental value is 0.2690 m /mol (Perry).

The error is thus 2 %.

Other methods, similar to those shown for the critical temperature and pressure also exist and have

similar accuracy.

The critical properties of mixtures are often calculated as the molar average value of the individual

values. For example, the critical temperature of a mixture can be calculated as follows:

Please note that x is the MOLE fraction and Tc(n) is the critical temperature of pure compound n.

propane = 369.8 K, iso-butane = 408.2 K, n-butane = 425.2 K

Tc (LPG) = 0.7 * 369.8 + 0.2 * 408.2 + 0.1 * 425.2 = 383.0 K

propane = 42.5 bar, iso-butane = 36.5 bar, n-butane = 38.0 bar

Pc (LPG) = 0.7 * 42.5 + 0.2 * 36.5 + 0.1 * 38.0 = 40.9 bar

The boiling point is defined as the temperature at which the vapour pressure of the liquid is equal to

the pressure of one atmosphere on the liquid i.e. the temperature at which the vapour pressure is

101325 Pa. However, if two values of vapour pressure close to 1 atm are available, the normal boiling

point can be interpolated or extrapolated. This is discussed in more detail in the section on vapour

pressures.

The normal boiling point is often published together with critical constants. Good sources for the

normal boiling point include:

th

Perrys Chemical Engineers Handbook, 7 Ed. Chapter 2

th

Properties of Gases and Liquids 4 Ed., Appendix A (p 568 et seq.)

CRC Handbook of Physics and Chemistry, Chapter 3 and Chapter 6

In addition, some suppliers of fine chemicals, such as Sigma-Aldrich, often give the melting points of

their compounds in their catalogues. Caution should be exercised when using values from older

sources since the temperatures were often reported at prevailing conditions (0.95 0.97 atm).

A number of correlations exist linking the critical temperature and the normal boiling point. Some of

these relationships have been discussed in section 2.1 and should the critical temperature be

available, the normal boiling point can be determined.

The normal boiling point can also be determined from the vapour pressure curve by setting the

pressure equal to 101325 Pa and solving the temperature. The vapour pressure curve is discussed in

section 3.

Steil and Thodos proposed a method to calculate the boiling points of normal hydrocarbons:

1163

Tb = 1209

(

1 + 0.0742 N0.85 ) (K ) (9)

Example: Normal boiling point of decane (10 carbon atoms) according to the method of Steil and

Thodos

1163

Tb = 1209 = 446K

(

1 + 0.0742 10 0.85 )

The experimental value is 447.3 K (Reid and Prausnitz).

The error is thus less than 0.5 %.

The accuracy of correlations such as those of Steil and Thodos are quite good but, as is the case with

the correlation of Steil and Thodos, these types of correlations are often limited to a few compounds.

A number of group contribution methods exist to predict the normal boiling point. Constantinou and

Gani also proposed such a group contribution method, this method being very similar to the ones for

estimating the critical temperature and the critical pressure. The normal boiling point can be estimated

as follows:

Tb

204 .359

= ln ( n Tbi ) (10)

Where Tbi is the contribution of the functional group (i) and n the number of groups (i) present. The

values of Tbi are given in Table 2 in section 9.2.

Example: Estimate the normal boiling point of octanoic acid according to the method of Constantinou

and Gani

There is 6 CH2 group, i.e. 6 * 0.9225

There is 1 COOH group, i.e. 5.8337

The right hand side of equation 10 is thus 12.2581.

Solving for Tb in equation 10 the normal boiling point is 512 K.

The published experimental value is 512 K !

The acentric factor () is a measure of the shape of a molecule, though it also measures its polarity.

The acentric factor is often used as a parameter in equations of state, hence its importance in

thermodynamics and chemical engineering. By definition, the acentric factor is calculated from the

reduced pressure at a reduced temperature of 0.7:

( )

= log Prsat Tr =0.7 1.000 (dim ensionless ) (11)

Critical pressures and temperatures are estimated according to the aforementioned methods. The

vapour pressure can be predicted according to the methods set out below or obtained experimentally.

For small, spherical molecules the acentric factor is essentially zero and it increases as branching,

molecular weight and polarity increases. For mixtures, the acentric factor is usually taken as the

simple molar average value of the compounds in the mixture:

n

= x i i (12)

i=1

Example: Calculate the acentric factor of the LPG mixture given above

Pure component acentric factors:

propane = 0.153, iso-butane = 0.183, n-butane = 0.199

(LPG) = 0.7 * 0.153 + 0.2 * 0.183 + 0.1 * 0.199 = 0.164

The acentric factor is usually published together with the critical constants of a compound.

The vapour pressure at a set temperature is the pressure exerted by a pure component at equilibrium

at this temperature when both liquid and vapour phases exist. The vapour pressure is a continuous

function of temperature and the vapour pressure curve extends from the triple point to the critical

point.

Vapour pressures have been measured extensively, usually as part of thermophysical data of a

compound. Perrys Chemical Engineers Handbook contains a large amount of the thermophysical

data. Another useful source of vapour pressure data is the NIST website. (See section 6).

sat

If the natural logarithm of the vapour pressure (ln(P )) is plotted as a function of the reciprocal of

temperature (1/T) the relationship is often linear over a limited temperature range. This is shown in

Figure 2.

6

4

2

ln(Psat) (ln(bar))

0 Ethane

-2 Hexane

Methane

-4

Nitrogen

-6

Water

-8

-10

-12

0.000 0.004 0.008 0.012 0.016

1/T (1/K)

sat

Figure 2: Relationship between 1/T and ln(P ) for ethane, hexane, methane, nitrogen and water

(Data from NIST Website)

sat

If a linear relationship between ln(P ) and 1/T is assumed, the vapour pressure curve can be

expressed as follows:

( )

ln P sat = m

1

T

+c (13)

This is probably the simplest method for predicting the vapour pressure or for interpolating (and to a

limited extent extrapolating) values. If two values on the vapour pressure curve are know, this method

can be used. Referring to equation 13:

m=

( ) ( )

ln P1sat ln P2sat

(14)

1 1

T1 T2

( )

c = ln P1sat m

1

T1

(15)

Using equations 14 and 15, equation 13 can now be used to determine the vapour pressure.

o

Example: Estimate the vapour pressure of propane at 0 C by interpolating between two values

sat

Given: Tb = 231.03 K, P (300.00 K) = 9.9780 bar

( )

At normal boiling point (Conditions 1): ln P1sat = 11.526 and 1/T1 = 0.004328

At 300.1 K (Conditions 2): ( ) = 13.813 and 1/T

ln P2sat 2 = 0.003333

11.526 13.813

m= = 2298

0.004328 0.003333

c = 11.526 ( 2298 ) 0.004328 = 21.474

( )

Therefore: ln P sat = 2298

1

T

+ 21.474 , T in K, P in Pa

o

At 0 C, i.e. 273.15 K:

( )

ln P sat = 2298

1

273.15

+ 21.474 = 13.06

sat

P = 469863 Pa = 4.70 bar.

The NIST website gives the value as 4.75 bar.

The error is thus less than 1.3 %

The Antoine equation is based on the same concept, yet due to the introduction of an additional

parameter is more accurate:

Antoine

( )

ln P sat = A +

B

T+C

(16)

A, B and C are regression constants and are unique to each compound. Table 5 in section 9.4 lists the

parameters for some compounds.

o

Example: Estimate the vapour pressure of carbon tetrachloride at 37 C using the Antoine equation

A = 15.8742

B = -2808.19

C = -45.99

o

At 37 C (308 K)

( )

ln P sat = 15.8742

2808 .19

310 45.99

= 5.2375

sat

Therefore P = 188.2 mmHg 25.1 kPa

The experimental value is 25.1 kPa !

However, the Antoine equation does not fit the data accurately much above the normal boiling point.

More accurate regression equations are required. These functions usually express the natural

logarithm of the vapour pressure as a function of temperature. Different sources use different

equations. Reid and Prausnitz use three correlations to estimate vapour pressure data for more than

500 compounds. The vapour pressure of these compounds can be expressed by one of three

equations:

P sat Ax + Bx 1.5 + Cx 3 + Dx 6

ln = (17)

P

c

(x 1)

where

T

x = 1 (18)

Tc

Reid and Prausnitz Equation 2

( )

ln P sat = A

B

T

+ C ln(T ) +

D P sat

T2

(19)

( )

ln P sat = A

B

T+C

(20)

The values of A, B and C are given in Properties of Gases and Liquids by Reid and Prausnitz (On

sat

reserve in the Library). The correlations use T in K and P in bar.

Equation 3 (equation 20) is in essence the Antoine equation. (See above for example). In equation 1

the pressure is calculated explicitly as a complex function of temperature. On the other hand, equation

2 needs to be solved iteratively. Examples of both equations 1 and 2 follow:

Example: Plot the vapour pressure curve from 260 to 430 K for 2,2-Dimethyl-propane using the

correlation in Reid and Prausnitz

Tc = 433.8 K, Pc = 32.0 bar

Using the above the vapour pressure was calculate and plotted: ln(Psat) is

plotted as a function of 1/T and compared to data from the NIST website:

3.5

NIST data

3

ln(Psat) with Psat in bar

2.5

2

1.5

1

0.5

0

-0.5

-1

0.002 0.0025 0.003 0.0035 0.004

1/T with T in K

As seen, the data generated with the correlation by Reid and Prausnitz

agrees very well with the data on the NIST website

Example: Estimate the vapour pressure of trichlorofluoromethane at 400 K using the correlation

published in Reid and Prausnitz

Correlation 2:

A = 42.089, B = 4464.14, C = -4.753, D = 2138 (P in bar, T in K)

Tc = 471.2 K, Pc = 44.1 bar

For 400 K:

P guess LHS RHS Ratio Change

20 2.9957 2.7185 1.1020 Increase Guess

25 3.2189 2.7853 1.1557 Decrease Guess

15 2.7081 2.6517 1.0213 Decrease Guess

14 2.6391 2.6383 1.0003 Decrease Guess

13.9 2.6319 2.6370 0.9981 Increase Guess

13.95 2.6355 2.6376 0.9992 Increase Guess

13.98 2.6376 2.6380 0.9998 Increase Guess

13.99 2.6383 2.6382 1.0001 Close enough

The NIST website gives the value as 14.074 bar.

The accuracy is thus 0.6 %.

Perry

( )

ln P sat = C1 +

C2

T

+ C 3 ln(T ) + C 4 T C5 (21)

th

The values of C1, C2, C3, C4 and C5 are given by Perry (page 2-50 2-54 in Table 2-6, 7 Edition).

The correlations use T in K and P in Pa.

Example: Plot the vapour pressure curve of hydrogen sulphide between 200 and 350 K using the

correlation in Perry

Using the above the vapour pressure was calculate and plotted: ln(Psat) is

plotted as a function of 1/T and compared to data from the NIST website:

16 Perry

NIST

15

ln(Psat) (Psat in Pa)

14

13

12

11

10

0.0025 0.003 0.0035 0.004 0.0045 0.005

1/T (T in K)

As seen, the data generated with the correlation by Perry agrees very well

with the data on the NIST website

The above methods all estimate the vapour pressure by correlating experimental values and fitting

them to a mathematical expression. Lee and Kesler proposed a method to estimate the vapour

pressure using only the critical temperature and pressure and the acentric factor of the compound as

parameters.

(

ln Prsat = ln Prsat )( ) + (lnP )( )

0

r

sat 1

(22)

Where

r

sat 0

T

1.28862 ln T + 0.169347 T

r r

6

(23)

r

r

sat 1

r + 0.43577 Tr

6

(24)

r

This method can be applied at reduced temperatures above 0.3 or above the melting point, whichever

is higher and below the critical point and is most reliable between reduced temperatures of 0.5 and

0.95.

o

Example: Estimate the vapour pressure of 1-butene at 98 C

o

Pure component parameters: Tc = 146.4 C, Pc = 4.02 MPa, = 0.1867

Tr =

(98 + 273.1) = 371.1 = 0.885

(146.4 + 273.1) 419.5

From equation 23:

(

ln Prsat) (0 )

= 5.92714

6.09648

0.885

1.28862 ln 0.885 + 0.169347 0.885 6

= 0.7227

From equation 24:

(

ln Prsat) (1)

= 15.2518

15.6875

0.885

13.4721 ln 0.885 + 0.43577 0.885 6

= 0.6190

From equation 22:

ln Prsat = 0.7227 + 0.1867 ( 0.6190 ) = 0.8383

Prsat = 0.4325

P sat = Prsat Pc

= 0.4325 4.02 = 1.74 MPa

Perry gives an experimental value of 1.72 MPa.

The error is thus 1.2 %

4 THERMAL PROPERTIES

Heat capacity is defined as the amount of energy required to change the temperature of a unit of mass

or mole by one degree. Typical units include J/mol.K and J/kg.K. Heat capacity is usually given either

at constant pressure (Cp) or at constant volume (Cv). Although heat capacity at constant volume is

sometimes used, most engineering applications use heat capacity at constant pressure and we will

thus focus on heat capacity at constant pressure.

In thermodynamics and in heat transfer the heat capacity is often used as a function of temperature in

the definition of enthalpy:

dh = Cp dT (25)

It is thus very useful if the heat capacity is expressed as a function of temperature.

A number of literature sources publish correlations which can be used to determine the heat capacity.

These sources include but are not limited to:

th

Perrys Chemical Engineers Handbook, 7 Edition, Chapter 2

th

Properties of Gases and Liquids 4 Edition, Appendix A

th

Basic Principles and Calculations in Chemical Engineering, 6 Edition

JANNAF Tables

When using such correlations, one needs to take note of the phase that the correlation refers to as

well as the temperature limits of the correlation.

There are also a number of sources that publish values of the heat capacity and / or enthalpy at

specific temperatures and pressures. The sources include but are not limited to:

Steam Tables

th

Perrys Chemical Engineers Handbook, 7 Edition, Chapter 2

This section focuses on energy changes without phase changes. For the energy associated with

phase changes, please see section 4.2.

Harrison and Seaton proposed a method, valid from 300 to 1500 K, to calculate the heat capacity of

an ideal gas based in the type and number of atoms in the molecule:

p ( J / mol) = a1 + a 2n C + a 3nH + a 4nO + a 5nN + a 6n S + a 7nF + a 8nCl + a 9nI

Cig

(26)

+ a10 nBr + a11nSi + a12n Al + a13 nB + a14nP + a15 nOther

Where a1 to a15 are constant parameters (See section 1.1 in Table 6) and ni are the number of atoms

of type i.

Example: Estimate the ideal gas heat capacity of acetone (C3H6O) at 600 K

C ig

p =-4.61 + 17.5 * 3 + 10.5 * 6 + 17.5 * 1 = 128 J/mol.K

Daubert et al. reported the experimental value as 121.8 J/mol.K.

The error is thus 5.5 %

However, the method of Harrison and Seaton is limited to ideal gases and does not provide the heat

capacity as an explicit function of temperature. Rihani and Doraiswamy suggested a group

contribution method to determine the heat capacity of vapours as a function of temperature. The heat

capacity has the following temperature functionality:

C p = a + bT + cT 2 + dT 3 (27)

a = n ai (28)

b = n bi (29)

c = n ci (30)

d = n di (31)

The group contribution parameters of ai, bi, ci and di are given in Table 7 to Table 12 in section 1.1 for

the unit cal/mol.K. Note the units and that the values are often multiplied by a power of 10 to give

reasonable values in the table.

Example: The vapour heat capacity of 3-methyl-1,2-butaniene as a function of temperature and at 300

K according to the method of Rihani and Doraiswamy

CH3

H2C C C

/

Therefore

a = 2 * 0.6087 + 2.6308 = 3.8483

b = 2 * 2.1433E-2 + 4.1658E-2 = 8.4524E-2

c = 2 * (-0.0852)E-4 + (-0.2845)E-4 = -0.4549E-4

d = 2 * 0.001135E-6 + 0.007277E-6 = 0.009547E-6

C p = 3.8483 + 0.084524 T 0.4549 10 4 T 2 + 0.9547 10 8 T 3 (cal/mol.K)

Using the correlation above the heat capacity at 300 K is estimated to be

25.37 cal/mol.K. The literature value (Weast) is 25.3 cal/mol.K. The error is

thus 0.3 %

Shaw proposed a group contribution method to estimate the liquid heat capacity at constant pressure

o

at 25 C:

Shaw

C p = nC pi (32)

Where Cpi is the contribution of functional group (i) and n the number of groups (i) present. The values

of Cpi are given in Table 13 in section 9.7.

Example: Estimate the heat capacity of hexane and heptane at 298.15 K using the method of Shaw

Hexane:

Two CH3 groups, i.e. 8.80 * 2 = 17.60

Four CH2 groups, i.e. 7.26 * 4 = 29.04

Cp = 17.60 + 29.04 = 46.6 cal/mol.K

This NIST website gives the value as 46.379 cal/mol.K

The error is thus 0.5 %

Heptane:

Two CH3 groups, i.e. 8.80 * 2 = 17.60

Four CH2 groups, i.e. 7.26 * 5 = 36.30

Cp = 17.60 + 36.30 = 53.9 cal/mol.K

This NIST website gives the value as 53.657 cal/mol.K

The error is thus 0.5 %

o

The method of Shaw, although simple and quite accurate is limited to 25 C. Rika and Domalski

proposed a group contribution method that is able to express the heat capacity of liquids as a second

order polynomial function of temperature. The method is applicable between the melting temperature

and the normal boiling temperature yet extrapolation of up to 80 K beyond the range has no

considerable effect.

2

Cp T T

= a+b + d (33)

R 100 100

a = n ai (34)

b = n bi (35)

d = n di (36)

The temperature is in K and the unit of Cp then depends in the unit of R. The values of ai, bi and di for

linear aliphatic and aromatics hydrocarbons are given in Table 14 in section 9.8. Parameters for

halogen, nitrogen, oxygen and sulphur groups are given in Table 15 in section 9.8. The method can be

extended to include second order interactions. This is beyond the scope of this course. (If required,

please consult the original texts [2,3].)

Example: Determine a temperature dependent correlation for the heat capacity of hexane and

estimate the heat capacity at 298.15 K

aCH3 = 3.8452 * 2 = 7.6904

bCH3 = -0.33997 * 2 = -0.67994

dCH3 = 0.19489 * 2 = 0.38979

aCH2 = 2.7972 * 4 = 11.1888

bCH2 = -0.054967 * 4 = -0.219868

dCH2 = 0.10697 * 4 = 0.42788

2

Cp T T

= 18.879 0.89981 + 0.81767

R 100 100

T T

2

C p = 8.314 18.879 0.89981 + 0.81767 J

100 100 mol.K

At 298.15 K:

2

Cp = 8.314 18.879 0.89981 + 0.81767

100 100

= 195.1 J

mol.K

The NIST website gives a value of 194.0 J/mol.K

The error is thus 0.5 %

As a first approximation the heat capacity of mixtures can be approximated by calculating the molar

average of the constituent compounds:

n

Cp (T ) = x iCpi (T ) (37)

i=1

This method works similar to the above discussed group contribution methods yet does not take

enthalpy of mixing into account. For accurate approximations, the enthalpy of mixing needs to be

incorporated.

When a substance changes phase, the enthalpy of the substance changes. This section concerns

itself with the energy associated with phase changes.

The enthalpy of vapourisation (hvap) is defined as the difference in the enthalpies of a unit of mole or

mass of a saturated vapour and a saturated liquid of a pure component. Basically, the enthalpy of

vapourisation is the energy required to vapourise a unit of mole or mass at the said temperature.

Similarly, the enthalpy of vapourisation is the amount of energy released when a unit mole or mass is

condensed at the said temperature.

Enthalpies of vapourisation are often published together with saturated enthalpies in sources such as

the steam tables and Perry.

Pitzer et al. proposed a method based in the corresponding states approach that only requires the

critical temperature and acentric factor:

Pitzer et al.

h vap

= 7.08(1 Tr ) + 10.95 (1 Tr )

0.354 0.456

(38)

RTc

Example: Estimate the enthalpy of vapourisation for propionaldehyde at 350 K using the method of

Pitzer et al.

From equation 38:

h vap

= 7.08(1 0.6939 ) + 10.95 0.2559 (1 0.6993 ) = 6.289

0.354 0.456

RTc

Thus:

hvap = 6.289 * 8.314 * 504.4 = 2.64 E4 J/mol 26.4 J/kmol

The experimental value is 26.85 (Perry) and the error is thus less than 2 %

Riedel proposed a method of estimating the enthalpy of vapourisation at the normal boiling point:

Reidel

Pc

ln 1

Tb 101.325

h vap, b = 1.039 R Tc (39)

Tc T

0.930 b

Tc

In equation 39, the critical pressure is in kPa and the critical temperature in K.

Example: Estimate the heat of vapourisation at the normal boiling point for ethyl acetate using the

method of Reidel

Therefore:

3880

ln 1

h vap,b = 1.039 8.314 523.3

350.2

101.325

523 .3 0.930 350 .2

523 .3

= 3.228 E4 J / mol = 32.28 kJ / mol

The experimental value is 32.23 kJ/mol (Perry).

The error is thus 0.16 %

Constantinou and Gani proposed a group contribution method to calculate the enthalpy of

vapourisation at 298 K:

h vap,298K = 6.892 + n h vi (kJ/mol) (40)

Where n is the number of functional groups (i) present and hvi the contribution of groups (i) present.

The values of hvi are given in 9.2 in Table 3.

Example: Estimate the enthalpy of vapourisation of methanol at 298 K according to the method of

Constantinou and Gani

There is one OH group, i.e. 24.529

Using equation 40:

h vap,298K = 6.892 + 4.116 + 24.529 = 35.537 kJ/mol

The NIST website gives the value as 37.466 kJ/mol.

The error is thus 5 %

The enthalpy of vapourisation decreases with temperature and is zero at the critical point. If the value

of the enthalpy of vapourisation is know at one point, the method of Watson can be used to describe

the enthalpy of vapourisation at any other temperature:

Watson

0.38

1 Tr,1

h vap,2 = h vap,1 (41)

1 T

r,2

Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450.0 K using the normal boiling

point as reference and using the method of Watson

Tr,2 = 450.0/523.3 = 0.8599

Therefore according to equation 41:

0.38

1 0.8599

h vap,2 = 32.23 = 23.25 kJ / mol

1 0.6692

The experimental value is 23.16 kJ/mol (Perry).

The error is thus 0.4 %

Perry also published correlations for the heats of vapourisation for over 230 compounds. The heat of

vapourisation is listed as a function of temperature:

Perry

C 2 + C3 Tr + C 4 (Tr )2

h f = C1 (1 Tr ) (42)

Where C1 through C4 are component specific parameters, listed in table 2-193 page 2-156 to 2-160

th

(7 Edition)

Example: Estimate the enthalpy of vapourisation for ethyl acetate at 450 K using the method of Perry

C1 = 4.933E7

C2 = 0.3847

C3 = C 4 = 0

Tr = 450.0 / 523.3 = 0.8599

h f = 4.933E7(1 0.8599 ) = 2.32E7 J / kmol = 23.2 kJ/mol

0.3847

The enthalpy of fusion hfus is defined as the difference of the enthalpies of a unit mole or mass of a

solid and liquid at its melting temperature and one atmosphere of pressure. Basically, the enthalpy of

fusion is the amount of energy required to melt a solid at its melting temperature and one atmosphere

of pressure. Similarly, the enthalpy of fusion is the amount of energy released when a liquid solidifies

at its melting temperature and one atmosphere of pressure. Perry list the enthalpy of fusion for a

number of compounds.

Correlations regarding the enthalpy of fusion are not as accurate as those for the enthalpy of

vapourisation and generally rely on group contribution methods. These group contribution methods

are complicated and beyond the scope of this course. (For additional reading see page 2-250 and the

th

tables on pages 2-252 and 2-253 in Perry, 7 Edition).

The enthalpy of formation is the energy required to form the compound at a specific temperature

(usually at 298 K) from its elements. The enthalpy of formation is often used in chemical reaction

thermodynamics, hence its importance here. The enthalpy of formation of a number of compounds is

listed in sources such as Physical Chemistry Textbooks and in Properties of Gases and Liquids by

Reid and Prausnitz. However, on occasion the values are not available and need to be estimated.

Constantinou and Gani proposed a group contribution method to calculate the enthalpy of formation at

298 K:

h f ,298K = 10.835 + n h fi (kJ/mol) (43)

Example: Estimate the standard (298 K) enthalpy of formation for ethanol using the method of

Constantinou and Gani

There is one CH2 group, i.e -20.763

There is one OH group, i.e. -181.422

Using equation 43:

h f ,298K = 10.835 45.947 20.763 181.422 = 237 .30 kJ/mol

Atkins gives the value as -235.10 kJ/mol.

The error is thus 1 %.

Note: This value is the standards energy of formation in the VAPOUR phase.

If you want to calculate the standard energy of formation in the liquid phase,

you need to take the heat of vaporisation at 298 K into account.

The heat of formation can also be estimated from the heats of combustion (if available). This method

is quite useful, especially for organic compounds containing N, S, O etc.

Example: Estimate the heat of formation for liquid ethanol using heat of combustion of ethanol

2 C (graphite) + 1/2 O2 (g) + 3 H2 (g) C2H6O (liq)

Consider the combustion reactions of C, H2, and CH3NO2:

C(graphite) + O2 (g) CO2 (g) hc = - 393.5 kJ/mol R1

H2 (g) + 1/2 O2 (g) H2O (liq) hc = - 285.8 kJ/mol R2

C2H6O (liq) + 3 O2 (g) 2 CO2 (g) + 3 H2O (liq)

hc = -1366.8 kJ/mol R3

Consider 2 * R1 + 3 * R2 R3:

Chemical reaction same as the formation reaction

hf = 2 * (-393.5) + 3 * (-285.8) (-1366.8) = -277.6 kJ/mol

The literature value is 277.6 kJ/mol

Remember, this is for LIQUID ethanol, because that is the way the reactions

are set up!

Similarly, Hesss Law together with information on other chemical reactions can be used to determine

the heat of formation. This was discussed in Engineering Chemistry 123.

5 PHYSICAL PROPERTIES

Most of the properties discussed above concern themselves with the thermodynamic and critical

properties of substances. These are the properties most commonly used in thermodynamics.

Substances do, however, also have a number of physical properties which are important in

engineering calculations, for example viscosity, thermal conductivity, diffusivity and surface tension.

The amount of data available regarding these properties varies and often, in the absence of reliable

experimental data, these properties need to be estimated. Estimation of these properties is beyond the

scope of this course yet similar methods as those used for the above discussed properties are used.

For further information consult sources such as Perrys Chemical Engineers Handbook and Properties

of Gases and Liquids.

6 WEB SOURCES

With the coming of the electronic age, a large amount of data is available electronically. However, due

to the abundance of data and ease of publication, one needs to exercise caution with unknown

sources. The American National Institute of Standards and Technology (NIST) has a website with very

reliable data. Thermodynamic and physical data for a number of pure components is available with

excellent accuracy and can be used with confidence. The website is accessible through the university

network at:

http://webbook.nist.gov/chemistry/fluid/

7 NOMENCLATURE

an Parameter in the Harrison and Seaton equation with n = 1 through 15

A Constant in the Antoine equation / Constant in the Reid and Prausnitz

vapour pressure correlation

b Coefficient of heat capacity equation

B Constant in the Antoine equation / Constant in the Reid and Prausnitz

vapour pressure correlation

c Intercept of the vapour pressure correlation / Coefficient of heat capacity

equation

C Constant in the Antoine equation / Constant in the Reid and Prausnitz

vapour pressure correlation

Cn Constants in vapour pressure / enthalpy of vapourisation correlation in

Perry with n = 1 through 5

Cp Heat capacity at constant pressure

Cv Heat capacity at constant volume

d Coefficient of heat capacity equation

D Constant in the Reid and Prausnitz vapour pressure correlation

h Enthalpy

hvi Contribution of group i to the enthalpy of vapourisation in the method

according to Constantinou and Gani.

hfi Contribution of group i to the standard enthalpy of fusion in the method

according to Constantinou and Gani.

m Gradient of the vapour pressure correlation

MW Molecular Mass

n Number of groups (i) in a group contribution method

ni The number of atoms of type i in a molecule (used in the Harrison and

Seaton equation)

N Number of carbon atoms in a linear hydrocarbon

R Gas constant

P Pressure

T Temperature

v Specific volume

x Temperature function used in the vapour pressure correlation

Z Compressibility

Acentric factor

Group contribution parameter for critical constants according to the

method of Lydersen / Fedors

hc Standard (298K, 1 atm) enthalpy of combustion

hf Standard (298K, 1 atm) enthalpy of fusion

hvap Enthalpy of vapourisation

Superscripts

ig Refers to the property of an ideal gas

sat Refers to the property at saturated conditions

Subscripts

1 Refers to the property at condition 1

2 Refers to the property at condition 2

298K Refers to the property at 298 K

b Refers to the property at the normal boiling point

bi Refers to the contribution of the group i to the normal boiling point

(Constantinou and Gani method)

c Refers to the property at the critical point

ci Refers to the contribution of the group i to the critical

temperature/pressure (Constantinou and Ganis method)

i Contribution of group i

m Refers to the property at the melting point

p Refers to the contribution of the group to the critical pressure (Lydersen

method)

r Refers to the reduced property

t Refers to the contribution of the group to the critical temperature

(Lydersen method)

v Refers to the contribution of the group to the critical volume (Fedors

method)

8 REFERENCES

The following general references are good sources of physical properties and their estimation:

th

[1] Perry, R.H.; Green, D.W. (Ed) (1997) Perrys Chemical Engineering Handbook, 7 Edition

(International Edition), McGraw-Hill

th

[2] Reid, R.C.; Prausnitz, J.M.; Poling, B.E. (1987) Properties of Gases and Liquids, 4 Edition,

McGraw-Hill

th

[3] Lide, D.R. (Ed.) (1997) CRC Handbook of Chemistry and Physics, 77 Edition, CRC Press

Other References

[1] Constantinou, L.; Gani, R. (1994) New Group Contribution Method for Estimating Properties of

Pure Compounds, AIChE Journal 40 (10) 1697 1710.

[2] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a

Function of Temperature Using Group Additivity. I. Hydrocarbon Compounds, Journal of

Physical and Chemical Reference Data 22 (3) 597 618.

[3] Rika, V.Jr.; Domalski, E.S.(1993) Estimation of the Heat Capacities of Organic Liquids as a

Function of Temperature Using Group Additivity. I. Compounds of Carbon, Hydrogen,

Halogens, Nitrogen, Oxygen, and Sulphur, Journal of Physical and Chemical Reference Data

22 (3) 619 655.

9 APPENDICES

Table 1: Group contribution paramters for the Lydersen method to calculate Tc and Pc

(From Perrys Chemical Engineers Handbook, page 2-343, Table 2-385)

9.2 Group contribution parameters for the Constantinou and Ganis method

Table 2: First order group contribution parameters for the estimation of critical properties and

normal boiling points for the method of Constantinou and Gani

(From AIChE Journal, volume 40, no 10, 1994, pages 1699 and 1700, Table 1)

Table 2 continued

Table 3: First order group contribution parameters for the estimation of thermodynamic

properties and normal boiling points for the method of Constantinou and Gani

(From AIChE Journal, volume 40, no 10, 1994, page 1700, Table 2)

9.3 Group increments for the Fedors method

Table 4: Group contribution parameters for the Fedors method to calculate vc

th

(From Perrys Chemical Engineers Handbook, 7 Edition page 2-344, Table 2-386)

Table 5: Constants for the Antoine equation to estimate the vapour pressure of some

compounds

th

(From Basic Principles and Calculations in Chemical Engineering, 6 Edition, page 669, Table G1)

NOTE: P in mmHg and T in K

9.5 Parameters for method of Harrison and Seaton

Table 6: Parameters for the method of Harrison and Seaton to calculate ideal gas heat capacity

(From Perrys Chemical Engineerss Handbook, page 2-348, Table 2-387)

9.6 Group contribution parameters for Rihani and Doraiswamys method

Table 7: Group contribution parameters for aliphatic hydrocarbon groups for estimation of

vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 18, Table 1)

Table 8: Group contribution parameters for aromatic hydrocarbon groups for estimation of

vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 18, Table 2)

Table 9: Group contribution parameters for contributions due to ring formation for estimation

of vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 3)

Table 10: Group contribution parameters for oxygen containing groups for estimation of

vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1 page 1965, Table 4)

Table 11: Group contribution parameters for nitrogen containing groups for estimation of

vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 5)

Table 12: Group contribution parameters for sulphur containing groups for estimation of

vapour heat capacities according to the method of Rihani and Doraiswamy

(From Industrial and Engineering Chemistry Fundamentals, volume 4 no 1, 1965, page 19, Table 6)

o

Table 13: Group contribution parameters for estimation of liquid heat capacity at 25 C

according to the method of Shaw

(From Journal of Chemical and Engineering Data, volume 14 no 4, page 464, Table 2)

9.8 Group contribution parameters for Rika and Domalskis method

Table 14: Group contribution parameters for linear hydrocarbon groups for estimation of liquid

heat capacities according to the method of Rika and Domalski

(From Journal of Physical and Chemical Reference Data, volume 22 no 3, page 604, Table 5)

Table 15: Group contribution parameters for halogen, nitrogen, oxygen and sulphur containing

groups for estimation of liquid heat capacities according to the method of Rika and

Domalski

(From Journal of Physical and Chemical Reference Data, volume 22 no 3, page 632 and 633, Table 8)

Table 15 continued

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