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Flow Measurement

and Instrumentation

www.elsevier.com/locate/ﬂowmeasinst

A procedure for the calculation of the natural gas molar heat capacity, the

isentropic exponent, and the Joule–Thomson coefﬁcient

Ivan Mari´ c

∗

Ru ¯ der Boškovi´ c Institute, Division of Electronics, Laboratory for Information Systems, Bijeniˇ cka c. 54, P.O.B. 180, 10002 Zagreb, Croatia

Received 22 March 2006; received in revised form 19 September 2006; accepted 14 December 2006

Abstract

A numerical procedure for the computation of a natural gas molar heat capacity, the isentropic exponent, and the Joule–Thomson coefﬁcient has

been derived using fundamental thermodynamic equations, DIPPR AIChE generic ideal heat capacity equations, and AGA-8 extended virial-type

equations of state. The procedure is implemented using the Object-Oriented Programming (OOP) approach. The results calculated are compared

with the corresponding measurement data. The ﬂow-rate through the oriﬁce plate with corner taps is simulated and the corresponding error due to

adiabatic expansion is calculated. The results are graphically illustrated and discussed.

c 2007 Elsevier Ltd. All rights reserved.

Keywords: Heat capacity; Joule–Thomson coefﬁcient; Isentropic exponent; Natural gas; Flow measurement

1. Introduction

When a gas is forced to ﬂow through a differential device

(see Fig. 1) it expands to a lower pressure and changes its

density. Flow-rate equations for differential pressure meters

assume a constant density of a ﬂuid within the meter. This

assumption applies only to incompressible ﬂows. In the case of

compressible ﬂows, a correction must be made. This correction

is known as the adiabatic expansion factor, which depends

on several parameters including the differential pressure, the

absolute pressure, pipe diameter, the differential device bore

diameter, and the isentropic exponent. The isentropic exponent

has a limited effect on the adiabatic correction factor, but needs

to be calculated if accurate ﬂow-rate measurements are needed.

When a gas expands through a restriction to a lower

pressure, it also changes its temperature. This process occurs

under the conditions of constant enthalpy and is known as

Joule–Thomson expansion [1]. It can also be considered as an

adiabatic effect, because the pressure change occurs too quickly

for signiﬁcant heat transfer to take place. The temperature

change is related to pressure change and is characterized by

the Joule–Thomson coefﬁcient. The temperature drop increases

∗

Tel.: +385 1 4561191; fax: +385 1 4680114.

E-mail address: ivan.maric@irb.hr.

with the increase of the pressure drop and is proportional to

the Joule–Thomson coefﬁcient. According to [2], the upstream

temperature is used for the calculation of ﬂow-rates, but

the temperature is preferably measured downstream of the

differential device. The use of downstream instead of upstream

temperatures may cause a ﬂow-rate measurement error due to

the difference in the gas density caused by the temperature

change. Our objective is to derive the numerical procedure for

the calculation of the natural gas speciﬁc heat capacity, the

isentropic exponent, and the Joule–Thomson coefﬁcient that

can be used to compensate for the adiabatic expansion effects

in real-time ﬂow-rate measurements.

2. Procedure

This section outlines the procedure for the calculation

of speciﬁc heat capacities at a constant pressure c

p

and

at a constant volume c

v

, the Joule–Thomson coefﬁcient

µ

JT

, and the isentropic exponent κ of a natural gas based

on thermodynamic equations, AGA-8 extended virial type

characterization equations [3,4], and DIPPR generic ideal heat

capacity equations [5]. First, the relation of the molar heat

capacity at constant volume to the equation of state will be

derived. Then the relation will be used to calculate a molar

heat capacity at constant pressure, which will then be used

0955-5986/$ - see front matter c 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.ﬂowmeasinst.2006.12.001

I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26 19

Fig. 1. Schematic diagram of the gas ﬂow-rate measurement using an oriﬁce plate with corner taps.

for the calculation of the Joule–Thomson coefﬁcient and the

isentropic exponent. The total differential for entropy, related

to temperature and molar volume [6], is:

ds =

∂s

∂T

v

m

dT +

∂s

∂v

m

T

dv

m

, (1)

where s denotes entropy, T denotes temperature, and v

m

is a

molar volume of a gas. By dividing the fundamental differential

for internal energy du = T · ds − p · dv

m

by dT while holding

v

m

constant, the coefﬁcient of dT in Eq. (1) becomes c

m,v

/T

since the molar heat at constant volume is deﬁned by c

m,v

=

(∂u/∂T)

v

m

. The Maxwell relation (∂s/∂v

m

)

T

= (∂p/∂T)

v

m

,

is used to substitute the coefﬁcient of dv

m

. Finally, the Eq. (1)

becomes:

ds =

c

m,v

T

dT +

∂p

∂T

v

m

dv

m

. (2)

Similarly, starting from a total differential for entropy related to

temperature and pressure [6] ds = (∂s/∂T)

p

dT+(∂s/∂p)

T

dp

and by dividing the fundamental differential for enthalpy dh =

T · ds +v

m

· dp by dT while holding p constant, the coefﬁcient

of dT in the total differential becomes c

m, p

/T, since the

molar heat capacity at constant pressure is deﬁned by c

m, p

=

(∂h/∂T)

p

. The Maxwell relation (∂s/∂p)

T

= (∂v

m

/∂T)

p

is used to substitute the coefﬁcient of dp and the following

relation is obtained:

ds =

c

m, p

T

dT +

∂v

m

∂T

p

dp. (3)

Subtracting Eq. (2) from Eq. (3), and then dividing the resulting

equation by dv

m

while holding p constant, and ﬁnally inverting

the partial derivative (∂T/∂v

m

)

p

, the following equation is

obtained:

c

m, p

− c

m,v

= T

∂v

m

∂T

p

∂p

∂T

v

m

. (4)

The total differential of the thermodynamic property

Eqs. (2) and (3) must be the exact differential, i.e. the order

of forming the mixed second derivative is irrelevant. The par-

tial derivative of the ﬁrst coefﬁcient with respect to the second

variable equals to the partial derivative of the second coefﬁcient

with respect to the ﬁrst variable. By applying this property to

Eq. (2) and by assuming T to be the ﬁrst variable with the cor-

responding coefﬁcient c

m,v

/T, and v

m

the second variable with

the corresponding coefﬁcient (∂p/∂T)

v

m

, we obtain:

∂c

m,v

∂v

m

T

= T

∂

2

p

∂T

2

v

m

. (5)

The Eq. (5) can be rewritten in the following integral form:

c

m,v

= c

m,vI

+ T

v

m

v

mI

→∞(T=const)

∂

2

p

∂T

2

v

m

dv

m

(6)

where c

m,vI

, v

mI

, and ν

m

denote the ideal molar heat capacity

at constant volume, the corresponding molar volume of the

ideal, and the real gas at temperature T respectively. Real gases

behave more like ideal gases as the pressure approaches zero or

v

mI

→ ∞. After substituting v

m

= 1/ρ

m

, p = RT Zρ

m

and

c

m,vI

= c

m, pI

− R, the Eq. (6) transforms to:

c

m,v

= c

m, pI

− R − RT

×

ρ

m

ρ

mI

→0(T=const)

1

ρ

m

2

∂ Z

∂T

ρ

m

+ T

∂

2

Z

∂T

2

ρ

m

dρ

m

(7)

where c

m, pI

denotes the temperature dependent molar heat

capacity of the ideal gas at constant pressure, R is the universal

gas constant, Z is the compression factor, and ρ

mI

and ρ

m

are

the corresponding molar densities of the ideal and the real gas

at temperature T. After substituting the ﬁrst and the second

derivative of the AGA-8 compressibility equation [4],

Z = 1 + Bρ

m

− ρ

r

18

¸

n=13

C

∗

n

+

58

¸

n=13

C

∗

n

b

n

− c

n

k

n

ρ

k

n

r

ρ

b

n

r

e

−c

n

ρ

kn

r

(8)

into the Eq. (7) and after integration we obtain

c

m,v

= c

m, pI

− R + RTρ

r

(2C

0

+ TC

1

− C

2

) (9)

20 I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26

with

C

0

=

18

¸

n=13

C

∗

n

−

B

K

3

(10)

C

1

=

18

¸

n=13

C

∗

n

−

B

K

3

(11)

C

2

=

58

¸

n=13

2C

∗

n

+ TC

∗

n

ρ

b

n

−1

r

e

−c

n

ρ

kn

r

(12)

where ρ

r

is the reduced density (ρ

r

= K

3

ρ

m

), B is the

second virial coefﬁcient,

¸

C

∗

n

¸

are the temperature dependent

coefﬁcients, K is the mixture size parameter, while {b

n

}, {c

n

},

and {k

n

} are the parameters of the equation of state. The mixture

size parameter K is calculated using the following equation [4]:

K

5

=

N

¸

i =1

y

i

K

5/2

i

2

+2

N−1

¸

i =1

N

¸

j =i +1

y

i

y

j

(K

5

i j

− 1)(K

i

K

j

)

5/2

, (13)

where y

i

denotes the molar fraction of the component i , while

{K

i

} and

¸

K

i j

¸

are the corresponding size parameters and the

binary interaction parameters given in [4]. According to [4],

the second virial coefﬁcient is calculated using the following

equation:

B =

18

¸

n=1

a

n

T

−u

n

N

¸

i =1

N

¸

j =1

y

i

y

j

B

∗

ni j

E

u

n

i j

(K

i

K

j

)

3/2

(14)

and the coefﬁcients

¸

B

∗

ni j

¸

,

¸

E

i j

¸

and

¸

G

i j

¸

are deﬁned by

B

∗

ni j

= (G

i j

+ 1 − g

n

)

g

n

(Q

i

Q

j

+ 1 − q

n

)

q

n

×(F

1/2

i

F

1/2

j

+ 1 − f

n

)

f

n

· (S

i

S

j

+ 1 − s

n

)

s

n

(W

i

W

j

+ 1 − w

n

)

w

n

, (15)

E

i j

= E

∗

i j

(E

i

E

j

)

1/2

(16)

and

G

i j

= G

∗

i j

(G

i

+ G

j

)/2, (17)

where T is the temperature, N is the total number of gas

mixture components, y

i

is the molar fraction of the component

i , {a

n

}, { f

n

}, {g

n

}, {q

n

}, {s

n

}, {u

n

}, and {w

n

} are the parameters

of the equation of state, {E

i

}, {F

i

}, {G

i

}, {K

i

}, {Q

i

}, {S

i

}, and

{W

i

} are the corresponding characterization parameters, while

¸

E

∗

i j

¸

and

¸

G

∗

i j

¸

are the corresponding binary interaction

parameters. The main symbols and units are given in Table 1.

For additional symbols and units refer to ISO-12213-2 [4]. The

temperature dependent coefﬁcients

¸

C

∗

n

; n = 1, . . . , 58

¸

and

the mixture parameters U, G, Q, and F are calculated using

the equations [4]:

C

∗

n

= a

n

(G + 1 − g

n

)

g

n

(Q

2

+ 1 − q

n

)

q

n

×(F + 1 − f

n

)

f

n

U

u

n

T

−u

n

, (18)

Table 1

Symbols and units (for additional symbols and units refer to ISO-12213-2 [4])

Symbols and units

Symbol Description Unit

B Second virial coefﬁcient m

3

∗ kmol

−1

B

∗

ni j

Mixture interaction coefﬁcient –

C Coefﬁcient of discharge –

c

m, p

Molar heat capacity at constant pressure J/(mol K)

c

m,v

Molar heat capacity at constant volume J/(mol K)

C

∗

n

Temperature and composition dependent

coefﬁcients

–

c

n

AGA-8 equation of state parameter –

c

p

Speciﬁc heat capacity at constant pressure J/(kg K)

c

m, pI

Ideal molar heat capacity of the natural gas mixture J/(mol K)

C

j

m, pi

Ideal molar heat capacity of the gas component j J/(mol K)

D Upstream internal pipe diameter m

d Diameter of oriﬁce m

h Speciﬁc enthalpy J/kg

K Size parameter –

p Absolute pressure Pa

q

m

Mass ﬂow-rate kg/s

R Molar gas constant 8314.51 J/(kmol K)

s Speciﬁc entropy J/(kg K)

T Absolute temperature K

v

m

Molar speciﬁc volume m

3

/kmol

v

mI

Molar speciﬁc volume of ideal gas m

3

/kmol

y

i

Molar fraction of i -th component in gas mixture –

Z Compression factor –

β Diameter ratio d/D –

p Differential pressure Pa

ω Pressure loss Pa

κ Isentropic exponent –

µ

JT

Joule–Thomson coefﬁcient K/Pa

ρ

m

Molar density kmol/m

3

ρ

mI

Molar density of ideal gas kmol/m

3

ρ

r

Reduced density –

U

5

=

N

¸

i =1

y

i

E

5/2

i

2

+2

N−1

¸

i =1

N

¸

j =i +1

y

i

y

j

(U

5

i j

− 1)(E

i

E

j

)

5/2

, (19)

G =

N

¸

i =1

y

i

G

i

+ 2

N−1

¸

i =1

N

¸

j =i +1

y

i

y

j

(G

∗

i j

− 1)(G

i

+ G

j

), (20)

Q =

N

¸

i =1

y

i

Q

i

, (21)

and

F =

N

¸

i =1

y

2

i

F

i

, (22)

where, U

i j

is the binary interaction parameter for mixture

energy. The ﬁrst and the second derivatives of the coefﬁcients

B and C

∗

n

, with respect to temperature, are:

B

= −

18

¸

n=1

a

n

u

n

T

−u

n

−1

N

¸

i =1

N

¸

j =1

y

i

y

j

B

∗

ni j

E

u

n

i j

(K

i

K

j

)

3/2

(23)

I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26 21

Table 2

The DIPPR/AIChE gas heat capacity constants

Natural gas component DIPPR/AIChE ideal gas heat capacity constants

a b c d e

Methane — CH

4

33 298 79 933 2086.9 41 602 991.96

Ethane — C

2

H

6

40 326 134 220 1655.5 73 223 752.87

Propane — C

3

H

8

51 920 192 450 1626.5 116 800 723.6

B

=

18

¸

n=1

a

n

u

n

(u

n

+ 1)T

−u

n

−2

×

N

¸

i =1

N

¸

j =1

y

i

y

j

B

∗

ni j

E

u

n

i j

(K

i

K

j

)

3/2

(24)

C

∗

n

= −

u

n

T

C

∗

n

(25)

C

∗

n

= −

u

n

+ 1

T

C

∗

n

. (26)

The ideal molar heat capacity c

pI

is calculated by

c

m, pI

=

N

¸

j =1

y

j

c

j

m, pi

(27)

where y

j

is the molar fraction of component j in the gas

mixture and C

j

m, pi

is the molar heat capacity of the same

component. The molar heat capacities of the ideal gas mixture

components can be approximated by the DIPPR/AIChE generic

equations [5], i.e.

c

j

m, pi

= a

j

+ b

j

c

j

/T

sinh(c

j

/T)

2

+ d

j

e

j

/T

cosh(e

j

/T)

2

,

(28)

where c

j

m, pi

is the molar heat capacity of the component j of the

ideal gas mixture, a

j

, b

j

, c

j

, d

j

, and e

j

are the corresponding

constants, and T is the temperature. The constants a, b, c, d,

and e for some gases are shown in Table 2.

The partial derivative of pressure with respect to temperature

at constant molar volume, and the partial derivative of molar

volume with respect to temperature at constant pressure, are

deﬁned by the equations:

∂p

∂T

v

m

= Rρ

m

[Z + T(C

3

− ρ

r

C

0

)] (29)

and

∂v

m

∂T

p

=

R

p

¸

Z +

∂ Z

∂T

p

T

(30)

where,

C

3

=

58

¸

n=13

C

∗

n

D

∗

n

, (31)

D

n

= (b

n

− c

n

k

n

ρ

k

n

r

)ρ

b

n

r

e

−c

n

ρ

kn

r

, (32)

∂ Z

∂T

p

=

R(T Z)

2

C

3

− pZ[T K

3

C

0

+ C

4

]

R(T Z)

2

+ pTC

4

, (33)

C

4

= C

5

+

58

¸

n=13

C

∗

n

D

1n

(34)

C

5

= B − K

3

18

¸

n=13

C

∗

n

(35)

and

D

1n

= K

3

[b

2

n

− c

n

k

n

(2b

n

+ k

n

− c

n

k

n

ρ

k

n

r

)ρ

k

n

r

]

×ρ

b

n

−1

r

e

−c

n

ρ

kn

r

. (36)

The isentropic exponent is deﬁned by the following relation

κ = −

c

m, p

c

m,v

∂p

∂v

m

T

v

m

p

= −

c

m, p

c

m,v

ρ

m

p

∂p

∂v

m

T

, (37)

where

∂p

∂v

m

T

=

∂p

∂ρ

m

T

∂ρ

m

∂v

m

T

= −RTρ

2

m

(Z + ρ

m

C

4

) . (38)

The Joule–Thomson coefﬁcient is deﬁned by the following

equation [2]:

µ

JT

=

RT

2

pc

m, p

∂ Z

∂T

p

. (39)

The derivation of the Eq. (39) is given in [6] and [7].

3. Implementation

The procedure for the calculation of the natural gas density,

compression, molar heat capacity, isentropic exponent, and the

Joule–Thomson coefﬁcient is implemented in the OOP mode,

which enables an easy integration into new software projects.

The interface to the software object is shown in Fig. 2. The

input/output parameters and functions are accessible, while

the internal structure is hidden from the user. The function

“Calculate” maps the input parameters (pressure, temperature,

and the molar fractions of natural gas components) into the

output parameters (density, compression, molar heat capacity,

isentropic exponent, and Joule–Thomson coefﬁcient). Table 3

depicts the calculation procedure. Prior to the calculation of

the molar heat capacities, the isentropic exponent, and the

Joule–Thomson coefﬁcient, the density and the compression

factor of a natural gas must be calculated. The false position

method is combined with the successive bisection method

to calculate the roots of the equation of state [4]. Using

CORBA [8] or DCOM [9], the component can be accessed

remotely.

22 I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26

Fig. 2. Interface to the software object that implements the calculation of the natural gas properties.

Table 3

The input/output parameters and the procedure for the computation of the

natural gas properties

Input parameters—constant:

• Molar gas constant (R = 8314.51 J/(kmol K))

• Natural gas equation of state parameters (a

n

, b

n

, c

n

, k

n

, u

n

, g

n

, q

n

, f

n

,

s

n

, w

n

; n = 1, 2, . . . , 58), characterization parameters (M

i

, E

i

, K

i

, G

i

,

Q

i

, F

i

, S

i

, W

i

; i = 1, . . . , 21) and binary interaction parameters (E

∗

i, j

,

U

i, j

, K

i, j

, G

∗

i, j

) (see ISO 12213-2)

• DIPPR/AIChE gas heat capacity constants (a

j

, b

j

, c

j

, d

j

, e

j

; j = 1, 2,

. . . , N)

Input parameters—time varying:

• Absolute pressure: p (MPa)

• Absolute temperature: T (K)

• Molar fractions of the natural gas mixture: y

i

; i = 1, 2, . . . , N

Calculation procedure:

1 Mixture size parameter K (Eq. (13)), second virial coefﬁcient

B (Eq. (14)) and temperature dependent coefﬁcients C

∗

n

(Eq. (18))

2 Compression factor Z (Eq. (8)) (see ISO-12213-2 for details of

calculation)

3 Molar density ρ

m

= p/RT Z, reduced density ρ

r

= K

3

ρ

m

and molar

volume v

m

= 1/ρ

m

.

4 Coefﬁcients D

n

and D

1n

(Eqs. (32) and (36))

5 1st and 2nd derivative of the second virial coefﬁcient B: B

(Eq. (23)) and

B

(Eq. (24))

6 1st and 2nd derivative of the coefﬁcient C

∗

n

: C

∗

n

(Eq. (25)) and

C

∗

n

(Eq. (26))

7 1st derivative of the compression factor Z : (∂ Z/∂T)

p

(Eq. (33))

8 Partial derivatives of pressure: (∂p/∂T)

v

m

(Eq. (29)) and (∂p/∂v

m

)

T

(Eq. (38))

9 Ideal molar heat capacity of a gas mixture at constant pressure: c

m, pI

(Eq. (27))

10 Molar heat capacity of a gas mixture at constant volume: c

m,v

(Eq. (9))

11 Molar heat capacity of a gas mixture at constant pressure: c

m, p

(Eq. (4))

12 Isentropic exponent κ (Eq. (37))

13 Joule–Thomson coefﬁcient µ

JT

(Eq. (39))

4. Application

We investigated the combined effect of the Joule–Thomson

coefﬁcient and the isentropic exponent of a natural gas on

the accuracy of ﬂow-rate measurements based on differential

devices. The measurement of a natural gas [4] ﬂowing in a

pipeline through an oriﬁce plate with corner taps (Fig. 1) is

assumed to be completely in accordance with the international

standard ISO-5167-2 [10]. The detailed description of the ﬂow-

rate equation with the corresponding iterative computation

scheme is given in [2] and [10]. The ﬂow-rate through the

oriﬁce is proportional to the expansibility factor, which is

related to the isentropic exponent. According to [10], the

expansibility factor ε for the oriﬁce plate with corner taps is

deﬁned by:

ε = 1 − (0.351 + 0.256β

4

+ 0.93β

8

)[1 − ( p

2

/p

1

)

1/κ

] (40)

where β denotes the ratio of the diameter of the oriﬁce to

the internal diameter of the pipe, while p

1

and p

2

are the

absolute pressures upstream and downstream of the oriﬁce

plate, respectively. The corresponding temperature change T

of the gas for the oriﬁce plate with corner taps is deﬁned by

T = T

1

− T

2

≈ µ

JT

( p

1

, T

2

)ω (41)

where T

1

and T

2

indicate the corresponding temperatures

upstream and downstream of the oriﬁce plate, µ

JT

( p

1

, T

2

) is

the Joule–Thomson coefﬁcient at upstream pressure p

1

and

downstream temperature T

2

, and ω is the pressure loss across

the oriﬁce plate [11], deﬁned by

ω =

1 − β

4

1 − C

2

− Cβ

2

1 − β

4

1 − C

2

+ Cβ

2

p (42)

where C denotes the coefﬁcient of discharge for the oriﬁce plate

with corner taps [10], and P is the pressure drop across the

oriﬁce plate. According to [2], the temperature of the ﬂuid shall

preferably be measured downstream of the primary device, but

upstream temperature shall be used for the calculation of the

ﬂow-rate. Within the limits of the application of ISO-5167 [2],

it is generally assumed that the temperature drop across the

differential device can be neglected, but it is also suggested that

it be taken into account if higher accuracies are required. It is

also assumed that the isentropic exponent can be approximated

by the ratio of the speciﬁc heat capacity at constant pressure

to the speciﬁc heat capacity at constant volume of the ideal

gas. The above approximations may produce a measurement

error. The relative ﬂow measurement error E

r

is estimated by

comparing the approximate (q

m2

) and the corrected (q

m1

) mass

ﬂow-rate i.e.

E

r

= (q

m2

− q

m1

) /q

m1

. (43)

I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26 23

Table 4

The procedure for the correction of the mass ﬂow-rate due to adiabatic

expansion effects

Step Description

1 Calculation of Joule–Thomson coefﬁcient µ

JT

( p

1

, T

2

) by using the

procedure outlined in Table 3 with upstream pressure p

1

and

downstream temperature T

2

2 Estimation of upstream temperature T

1

using the Eq. (41)

3 Calculation of density ρ = Mρ

m

and isentropic exponent κ using

the procedure outlined in Table 3 with upstream pressure p

1

and

estimated upstream temperature T

1

4 Calculation of viscosity (residual viscosity function) [12]

5 Calculation of mass ﬂow-rate in accordance with [10]

Fig. 3. Calculated and measured molar heat capacities at constant pressure of

the natural gas mixture.

Fig. 4. Calculated and measured Joule–Thomson coefﬁcients of the natural gas

mixture.

The individual and the combined relative errors due to the

approximations of the temperature drop and the isentropic

exponent are calculated. The procedure for the correction of the

mass ﬂow-rate due to the adiabatic expansion effects is shown

in Table 4. The calculation procedures are implemented in the

OOP mode. The results are presented in the following section.

Table 5

Difference between the calculated and measured speciﬁc heat capacity at

constant pressure of a natural gas

P (MPa): T (K) 250 275 300 350

(c

p calculated

− c

p measured

) (J/(g ∗ K))

0.5 −0.015 −0.018 −0.018 −0.012

1.0 −0.002 −0.014 −0.016 −0.011

2.0 −0.012 −0.019 −0.022 −0.020

3.0 −0.032 −0.020 −0.023 −0.026

4.0 −0.041 −0.023 −0.021 −0.027

5.0 −0.051 −0.022 −0.025 −0.029

7.5 −0.055 −0.032 – –

10.0 −0.077 −0.033 −0.048 −0.042

11.0 −0.075 – – –

12.5 −0.092 −0.030 – –

13.5 −0.097 −0.039 – –

15.0 −0.098 −0.033 −0.082 −0.069

16.0 – −0.036 – –

17.5 – −0.043 −0.075 –

20.0 −0.081 −0.048 −0.066 −0.134

25.0 −0.082 −0.033 −0.064 −0.171

30.0 −0.077 −0.025 −0.070 −0.194

Table 6

Difference between the calculated and measured Joule–Thomson coefﬁcient of

a natural gas

P (MPa): T (K) 250 275 300 350

(µ

JT calculated

− µ

JT measured

) (K/MPa)

0.5 −0.014 −0.023 −0.075 −0.059

1.0 −0.032 −0.024 −0.068 −0.053

2.0 – – – −0.051

3.0 −0.092 −0.032 −0.069 −0.049

5.0 −0.022 −0.036 −0.044 −0.026

7.5 0.043 – – –

10.0 0.060 0.096 0.019 0.030

12.5 0.034 – – –

15.0 0.113 0.093 0.050 0.061

20.0 0.029 0.084 0.009 0.047

25.0 0.025 0.059 0.002 0.043

30.0 0.031 0.052 0.005 0.012

5. Measurement results

In order to compare the calculation results, for the speciﬁc

heat capacity c

p

and the Joule–Thomson coefﬁcient µ

JT

, with

the corresponding high accuracy measurement data [13] (Ernst

et al.), we assume identical artiﬁcial natural gas mixtures with

the following mole fractions: x

CH

4

= 0.79942, x

C

2

H

6

=

0.05029, x

C

3

H

8

= 0.03000, x

CO

2

= 0.02090, and x

N

2

=

0.09939. The results of the measurements [13] and the

results of the calculation of the speciﬁc heat capacities c

p

and the Joule–Thomson coefﬁcients µ

JT

of the natural gas

mixtures, for absolute pressures ranging from 0 to 30 MPa

in 0.5 MPa steps and for four upstream temperatures (250,

275, 300, and 350 K), are shown in Fig. 3 and Fig. 4,

respectively. The differences between the calculated values and

the corresponding measurement results [13], for c

p

and µ

JT

,

are shown in Table 5 and Table 6, respectively. From Table 5,

it can be seen that the calculated values of c

p

are within

±0.08 J/(g ∗ K) of the measurement results for pressures up

24 I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26

to 12 MPa. At higher pressures, up to 30 MPa, the difference

increases, but never exceeds ±0.2 J/(g ∗ K). For pressures

up to 12 MPa, the relative difference between the calculated

and experimentally obtained c

p

never exceeds ±2.00%. From

Table 6, it can be seen that the calculated values of µ

JT

are

within ±0.113 K/MPa, with the experimental results for the

pressures up to 30 MPa. The relative difference increases with

the increase in pressure, but never exceeds ±2.5% for pressures

up to 12 MPa. At higher pressures, when the values of µ

JT

are

close to zero, the relative difference may increase signiﬁcantly.

The results of the calculations obtained for pure methane and

methane–ethane mixtures are in considerably better agreement

with the corresponding experimental data [13] than those for

the natural gas mixture shown above. We estimate that the

relative uncertainties of the calculated c

p

and µ

JT

of the

AGA-8 natural gas mixtures in common industrial operating

conditions (pressure range 0–12 MPa and temperature range

250–350 K) are unlikely to exceed ±3.00% and ±4.00%,

respectively. Fig. 5 shows the results of the calculation of

the isentropic exponent. Since the isentropic exponent is a

theoretical parameter, there exist no experimental data for its

veriﬁcation.

In order to simulate a ﬂow-rate measurement error caused

by an inappropriate compensation for the adiabatic expansion,

a natural gas mixture (Gas 3) form Annex C of [4] is

assumed to ﬂow through the oriﬁce plate with corner taps [9]

shown in Fig. 1. Following the recommendations [2], the

absolute pressure is assumed to be measured upstream ( p

1

),

and the temperature downstream (T

2

), of the primary device.

A natural gas analysis in mole fractions is the following:

methane 0.859, ethane 0.085, propane 0.023, carbon dioxide

0.015, nitrogen 0.010, i-butane 0.0035, n-butane 0.0035, i-

pentane 0.0005, and n-pentane 0.0005. Fig. 6 illustrates the

temperature drop due to the Joule–Thomson effect calculated

in accordance with Eq. (41). The results calculated are given

for two discrete differential pressures, p (20 and 100 kPa),

for absolute pressures p

1

ranging from 1 to 60 MPa in 1 MPa

steps, and for six equidistant upstream temperatures T

1

in the

range from 245 to 345 K. From Fig. 6 it can be seen that

for each temperature there exists the corresponding pressure

where the Joule–Thomson coefﬁcient changes its sign, and

consequently alters the sign of the temperature change. A

relative error in the ﬂow-rate measurements (Fig. 1) due to the

Joule–Thomson effect is shown in Fig. 7. The error is calculated

in accordance with Eq. (43) by comparing the approximate

mass ﬂow-rate (q

m2

) with the corrected mass ﬂow-rate (q

m1

).

The procedure for the precise correction of the mass ﬂow-

rate is shown in Table 4. The approximate ﬂow-rate and the

corresponding natural gas properties (density, viscosity, and

isentropic exponent) are calculated at upstream pressure p

1

,

downstream temperature T

2

, and differential pressure p, by

neglecting the temperature drop due to the Joule–Thomson

effect (T

2

= T

1

). The results are shown for two discrete

differential pressures p (20 and 100 kPa), for absolute

upstream pressures p

1

ranging from 1 to 60 MPa in 1 MPa

steps, and for four equidistant downstream temperatures T

2

in

the range from 245 to 305 K.

Fig. 5. Calculated isentropic exponent of the natural gas mixture.

Fig. 6. Temperature drop due to the Joule–Thomson effect T = µ

JT

ω

when measuring ﬂow-rate of the natural gas mixture through the oriﬁce plate

with corner taps (ISO-5167-2). The upstream pressure varies from 1 to 60 MPa

in 1 MPa steps and upstream temperature from 245 to 305 K in 20 K steps for

each of two differential pressures p (20 and 100 kPa). The internal diameters

of the oriﬁce and pipe are: d = 120 mm and D = 200 mm.

Fig. 7. Relative error E

r

= (q

m2

− q

m1

) /q

m1

in the ﬂow-rate of the natural

gas mixture measured by the oriﬁce plate with corner taps (ISO-5167-2) when

using downstream temperature with no compensation for the Joule–Thomson

effect (q

m2

) instead of upstream temperature (q

m1

). The upstream pressure

varies from 1 to 60 MPa in 1 MPa steps, and downstream temperature from

245 to 305 K in 20 K steps for each of two differential pressures p (20 and

100 kPa). The internal diameters of the oriﬁce and pipe are: d = 120 mm and

D = 200 mm.

I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26 25

Fig. 8. Relative error E

r

= (q

m2

− q

m1

) /q

m1

in the ﬂow-rate of the natural

gas mixture measured by the oriﬁce plate with corner taps (ISO-5167-2) when

using the isentropic exponent of the ideal gas (q

m2

) instead of the real gas

(q

m1

). The upstream pressure varies from 1 to 60 MPa in 1 MPa steps, and

downstream temperature from 245 to 305 K in 20 K steps, for each of two

differential pressures p (20 and 100 kPa). The internal diameters of the oriﬁce

and pipe are: d = 120 mm and D = 200 mm.

Fig. 8 illustrates the relative error in the ﬂow-rate

measurements due to the approximation of the isentropic

exponent by the ratio of the ideal molar heat capacities.

The error is calculated by comparing the approximate mass

ﬂow-rate (q

m2

) with the corrected mass ﬂow-rate (q

m1

) in

accordance with Eq. (43). The procedure for the precise

correction of the mass ﬂow-rate is shown in Table 4. The

approximate ﬂow-rate calculation is carried out in the same

way, with the exception of the isentropic exponent, which

equals the ratio of the ideal molar heat capacities (κ =

c

m, pI

/(c

m, pI

− R)). The results are shown for two discrete

differential pressures p (20 and 100 kPa), for absolute

upstream pressures p

1

ranging from 1 to 60 MPa in 1 MPa

steps, and for four equidistant downstream temperatures T

2

in

the range from 245 to 305 K.

Fig. 9 shows the ﬂow-rate measurement error produced

by the combined effect of the Joule–Thomson and the

isentropic expansions. The error is calculated by comparing the

approximate mass ﬂow-rate (q

m2

) with the corrected mass ﬂow-

rate (q

m1

) in accordance with Eq. (43). The procedure for the

precise correction of the mass ﬂow-rate is shown in Table 4.

The approximate ﬂow-rate and the corresponding natural gas

properties are calculated at upstream pressure p

1

, downstream

temperature T

2

, and differential pressure p, by neglecting the

temperature drop due to the Joule–Thomson effect (T

2

= T

1

)

and by substituting the isentropic exponent with the ratio of the

ideal molar heat capacities, κ = c

m, pI

/(c

m, pI

−R). The results

are shown for two discrete differential pressures p (20 and

100 kPa), for absolute upstream pressures p

1

ranging from 1 to

60 MPa in 1 MPa steps, and for four equidistant downstream

temperatures T

2

in the range from 245 to 305 K.

The results obtained for the Joule–Thomson coefﬁcient

and isentropic exponent are in complete agreement with

the results obtained when using the procedures described

in [7] and [14], which use natural gas fugacities to derive

the molar heat capacities and are, therefore, considerably

more computationally intensive and time consuming. The

Fig. 9. Relative error E

r

= (q

m2

− q

m1

) /q

m1

in the ﬂow-rate of the natural

gas mixture measured by an oriﬁce plate with corner taps (ISO-5167-2) when

using downstream temperature, with no compensation for the Joule–Thomson

effect and the isentropic exponent of the ideal gas at downstream temperature

(q

m2

) instead of upstream temperature, and the corresponding real gas

isentropic exponent (q

m1

). The upstream pressure varies from 1 to 60 MPa in

1 MPa steps and downstream temperature from 245 to 305 K in 20 K steps for

each of two differential pressures p (20 and 100 kPa). The internal diameters

of the oriﬁce and pipe are: d = 120 mm and D = 200 mm.

calculation results are shown up to a pressure of 60 MPa,

which lies within the wider ranges of application given

in [4], of 0–65 MPa. However, the lowest uncertainty for

compressibility is for pressures up to 12 MPa, and no

uncertainty is quoted in Reference [4] for pressures above

30 MPa. It would therefore seem sensible for the results of

the Joule–Thomson and the isentropic exponent calculations

to be used with caution above this pressure. From Fig. 9 it

can be seen that the maximum combined error is lower than

the maximum individual errors, because the Joule–Thomson

coefﬁcient (Fig. 7) and the isentropic exponent (Fig. 8) show

the countereffects on the ﬂow-rate error. The error always

increases by decreasing the operating temperature. The total

measurement error is still considerable, especially at lower

temperatures and higher differential pressures, and cannot be

overlooked. The measurement error is also dependent on the

natural gas mixture. For certain mixtures, like natural gases

with a high carbon dioxide content, the relative error in

the ﬂow-rate may increase up to 0.5% at lower operating

temperatures (245 K), and up to 1.0% at very low operating

temperatures (225 K). Whilst modern ﬂow computers have a

provision for applying a Joule–Thomson coefﬁcient and an

isentropic exponent correction to measured temperatures, this

usually takes the form of a ﬁxed value supplied by the

user. The calculations in this paper show that any initial error

in choosing this value, or subsequent operational changes

in temperature, pressure or gas composition, could lead to

signiﬁcant systematic metering errors. Our further work will be

directed towards the improvement of the model, with the aim

of simplifying the calculation procedure and further decreasing

the uncertainty of the calculation results.

6. Conclusion

This paper describes the numerical procedure for the

calculation of the natural gas molar heat capacity, the

26 I. Mari´ c / Flow Measurement and Instrumentation 18 (2007) 18–26

Joule–Thomson coefﬁcient and the isentropic exponent. The

corresponding equations have been derived by applying the

fundamental thermodynamic relations to AGA-8 extended

virial-type equations of state. The DIPPR AIChE generic

ideal heat capacity equations have been used to calculate the

ideal molar heat capacities of a natural gas mixture. The

implementation of the procedure in an OOP mode enables

its easy integration into new software developments. An

example of a possible application of the procedure in the

ﬂow-rate measurements has been given. The procedure can be

efﬁciently applied in both off-line calculations and real time

measurements.

Acknowledgements

This work has been supported by the Croatian Ministry of

Science, Education, and Sport with the projects “Computational

Intelligence Methods in Measurement Systems” and “Real-Life

Data Measurement and Characterization”. The author would

like to express his thanks to Professor Donald R. Olander,

University of California, Berkeley, USA, for his valuable

suggestions, and to Dr. Eric W. Lemmon, NIST, USA, for his

help in obtaining the relevant measurement data.

References

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devices inserted in circular-cross section conduits running full — Part 2:

General principles and requirements. Ref. No. ISO-51671-1:2003(E).

ISO; 2003.

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other hydrocarbon gases. Transmission measurement committee report

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2:1997(E). ISO; 1997.

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ics, Retrieved September 21, 2005, from Department of Nuclear En-

gineering, University of California: Berkeley [Chapter 7]. WEB site:

http://www.nuc.berkeley.edu/courses/classes/E-115/Reader/index.htm.

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heterogeneous environments. IEEE Communications Magazine 1997;

35(2):46–55.

[9] Microsoft: DCOM Architecture. White Paper. Microsoft Corporation.

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devices inserted in circular-cross section conduits running full — Part 2:

Oriﬁce plates. Ref. No. ISO-51671-2:2003(E). ISO; 2003.

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Measurement and Instrumentation 1997;8:39–41.

[12] Miller RW. The ﬂow measurement engineering book. 3rd ed. New York:

McGraw-Hill; 1996.

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the massic heat capacity cp and Joule–Thomson coefﬁcient of CH

4

, of

(0.85CH

4

+ 0.16C

2

H

6

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exponent. Flow Measurement and Instrumentation 2005;16(1):13–20.

v = cm. (1) becomes cm. for the calculation of the Joule–Thomson coefﬁcient and the isentropic exponent. 1. After substituting the ﬁrst and the second derivative of the AGA-8 compressibility equation [4]. the Eq. (2) ∂2 p ∂T 2 vm . T (1) variable equals to the partial derivative of the second coefﬁcient with respect to the ﬁrst variable. the order of forming the mixed second derivative is irrelevant. p − cm. After substituting vm = 1/ρm .v /T since the molar heat at constant volume is deﬁned by cm. Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c 19 Fig. (4) where cm. and vm the second variable with the corresponding coefﬁcient (∂ p/∂ T )vm . i. The Maxwell relation (∂s/∂vm )T = (∂ p/∂ T )vm . Real gases behave more like ideal gases as the pressure approaches zero or vm I → ∞.v I = cm. and then dividing the resulting equation by dvm while holding p constant.v dT + T ∂p ∂T dvm .v = cm. p I − R. (7) and after integration we obtain cm. By dividing the fundamental differential for internal energy du = T · ds − p · dvm by dT while holding vm constant.v = cm.e. related to temperature and molar volume [6]. By applying this property to Eq. and ﬁnally inverting the partial derivative (∂ T /∂vm ) p . The total differential for entropy. p /T . R is the universal gas constant. T denotes temperature. (5) can be rewritten in the following integral form: vm cm. (2) and (3) must be the exact differential. Z is the compression factor.v I + T vm I →∞(T =const) ∂2 p ∂T 2 vm dvm (6) vm Similarly. Finally.v = (∂u/∂ T )vm . (6) transforms to: cm.v = T ∂vm ∂T ∂p ∂T . the following equation is obtained: cm. we obtain: ∂cm.I. p I denotes the temperature dependent molar heat capacity of the ideal gas at constant pressure.v I . The Maxwell relation (∂s/∂ p)T = (∂vm /∂ T ) p is used to substitute the coefﬁcient of d p and the following relation is obtained: ds = cm. the coefﬁcient of dT in the total differential becomes cm. (2) and by assuming T to be the ﬁrst variable with the corresponding coefﬁcient cm. The partial derivative of the ﬁrst coefﬁcient with respect to the second into the Eq. starting from a total differential for entropy related to temperature and pressure [6] ds = (∂s/∂ T ) p dT +(∂s/∂ p)T d p and by dividing the fundamental differential for enthalpy dh = T · ds + vm · d p by dT while holding p constant. and ρm I and ρm are the corresponding molar densities of the ideal and the real gas at temperature T . the corresponding molar volume of the ideal. since the molar heat capacity at constant pressure is deﬁned by cm. the coefﬁcient of dT in Eq. vm I . (5) The Eq. Schematic diagram of the gas ﬂow-rate measurement using an oriﬁce plate with corner taps. (3). and the real gas at temperature T respectively. the Eq. 18 Z = 1 + Bρm − ρr n=13 58 ∗ Cn p vm + n=13 ∗ k b Cn bn − cn kn ρr n ρr n e−cn ρr kn (8) The total differential of the thermodynamic property Eqs. (2) from Eq. and νm denote the ideal molar heat capacity at constant volume. p = RT Zρm and cm. is used to substitute the coefﬁcient of dvm . p I − R − RT ρm × ρm I →0(T =const) 1 ρm 2 ∂Z ∂T +T ρm ∂2 Z ∂T 2 ρm dρm (7) (3) Subtracting Eq.v ∂vm =T T where s denotes entropy. and vm is a molar volume of a gas. p where cm. p = (∂h/∂ T ) p .v /T . (1) becomes: ds = cm. p dT + T ∂vm ∂T d p. is: ds = ∂s ∂T dT + vm ∂s ∂vm dvm . p I − R + RTρr (2C0 + T C1 − C2 ) (9) .

{Fi }. {G i }. E i j = E i∗j (E i E j )1/2 and ∗ G i j = G i j (G i + G j )/2. {cn }. i=1 j=i+1 (19) N G= (17) Q= i=1 i=1 N yi G i + 2 (20) where T is the temperature. pi D d h K p qm R s T vm vm I yi Z β p ω κ µJT ρm ρm I ρr where ρr is the reduced density (ρr = K 3 ρm ). (21) and N F= i=1 yi2 Fi . and F are calculated using the equations [4]: ∗ Cn = an (G + 1 − gn )gn (Q 2 + 1 − qn )qn × (F + 1 − f n ) fn U u n T −u n . {qn }. . { f n }. p cm. For additional symbols and units refer to ISO-12213-2 [4]. while {bn }. .51 Speciﬁc entropy Absolute temperature Molar speciﬁc volume Molar speciﬁc volume of ideal gas Molar fraction of i-th component in gas mixture Compression factor Diameter ratio d/D Differential pressure Pressure loss Isentropic exponent Joule–Thomson coefﬁcient Molar density Molar density of ideal gas Reduced density ∗ and the coefﬁcients Bni j . {Q i }. (13) where yi denotes the molar fraction of the component i. {u n }. while {K i } and K i j are the corresponding size parameters and the binary interaction parameters given in [4]. the second virial coefﬁcient is calculated using the following equation: 18 N N ∗ yi y j Bni j E iujn (K i K j )3/2 i=1 j=1 B= n=1 an T −u n (14) Second virial coefﬁcient Mixture interaction coefﬁcient Coefﬁcient of discharge Molar heat capacity at constant pressure Molar heat capacity at constant volume Temperature and composition dependent coefﬁcients AGA-8 equation of state parameter Speciﬁc heat capacity at constant pressure Ideal molar heat capacity of the natural gas mixture Ideal molar heat capacity of the gas component j Upstream internal pipe diameter Diameter of oriﬁce Speciﬁc enthalpy Size parameter Absolute pressure Mass ﬂow-rate Molar gas constant 8314. . E i j and G i j are deﬁned by ∗ Bni j = (G i j + 1 − gn )gn (Q i Q j + 1 − qn )qn N 2 5/2 yi E i N × (Fi F j + 1 − f n ) fn · (Si S j + 1 − sn )sn (Wi W j + 1 − wn )wn . p I j Cm. and {wn } are the parameters of the equation of state. {E i }. {an }. Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c Table 1 Symbols and units (for additional symbols and units refer to ISO-12213-2 [4]) ∗ Cn − n=13 18 with 18 C0 = B K3 B K3 b ρr n −1 e−cn ρr kn (10) Symbols and units Symbol Description Unit m3 ∗ kmol−1 – – J/(mol K) J/(mol K) – – J/(kg K) J/(mol K) J/(mol K) m m J/kg – Pa kg/s J/(kmol K) J/(kg K) K m3 /kmol m3 /kmol – – – Pa Pa – K/Pa kmol/m3 kmol/m3 – C1 = n=13 58 ∗ Cn − (11) C2 = n=13 ∗ ∗ 2Cn + T Cn (12) B ∗ Bni j C cm. N is the total number of gas mixture components. The ∗ temperature dependent coefﬁcients Cn .20 I. Ui j is the binary interaction parameter for mixture energy. and {kn } are the parameters of the equation of state. {sn }. (22) where. {K i }. are: 18 N N ∗ yi y j Bni j E iujn (K i K j )3/2 (23) i=1 j=1 B =− (18) n=1 an u n T −u n −1 . . yi is the molar fraction of the component i. The mixture size parameter K is calculated using the following equation [4]: N 2 5/2 yi K i N −1 N K = i=1 5 +2 i=1 j=i+1 yi y j (K i5j − 1)(K i K j )5/2 . Cn are the temperature dependent coefﬁcients. {Si }. {gn }. The main symbols and units are given in Table 1. Q. yi Q i . with respect to temperature. and {Wi } are the corresponding characterization parameters. i=1 j=i+1 N −1 N ∗ yi y j (G i j − 1)(G i + G j ). n = 1. 1/2 1/2 U (15) (16) 5 = +2 i=1 N −1 yi y j (Ui5j − 1)(E i E j )5/2 .v ∗ Cn cn cp cm. The ﬁrst and the second derivatives of the coefﬁcients ∗ B and Cn . while ∗ E i∗j and G i j are the corresponding binary interaction parameters. B is the ∗ second virial coefﬁcient. According to [4]. G. K is the mixture size parameter. 58 and the mixture parameters U .

and the partial derivative of molar volume with respect to temperature at constant pressure.I.5 1626. b. T The ideal molar heat capacity c p I is calculated by N and 2 k k D1n = K 3 [bn − cn kn (2bn + kn − cn kn ρr n )ρr n ] b × ρr n −1 e−cn ρr . 58 j where cm.6 B = n=1 an u n (u n + 1)T −u n −2 N N ∗ yi y j Bni j E iujn (K i K j )3/2 i=1 j=1 C4 = C5 + n=13 ∗ Cn D1n 18 (34) × ∗ Cn = − (24) (25) (26) C5 = B − K 3 n=13 ∗ Cn (35) un ∗ C T n un + 1 ∗ ∗ Cn = − Cn .e. Table 3 depicts the calculation procedure. p cm. and the molar fractions of natural gas components) into the output parameters (density.87 723.9 1655. The constants a.5 58 d 41 602 73 223 116 800 e 991. Implementation The procedure for the calculation of the natural gas density. pi is the molar heat capacity of the same component. The partial derivative of pressure with respect to temperature at constant molar volume. d j . and e for some gases are shown in Table 2.v ρm p ∂p ∂vm . and the Joule–Thomson coefﬁcient. R(T Z )2 + pT C4 . isentropic exponent.v ∂p ∂vm ∂p ∂ρm T vm p =− cm. Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c Table 2 The DIPPR/AIChE gas heat capacity constants Natural gas component Methane — CH4 Ethane — C2 H6 Propane — C3 H8 18 21 DIPPR/AIChE ideal gas heat capacity constants a b 33 298 40 326 51 920 79 933 134 220 192 450 c 2086. (38) c j /T sinh(c j /T ) 2 + dj e j /T cosh(e j /T ) 2 . pi j (27) κ=− where ∂p ∂vm cm. T (37) where y j is the molar fraction of component j in the gas j mixture and Cm. the component can be accessed remotely. (28) The Joule–Thomson coefﬁcient is deﬁned by the following equation [2]: µJT = RT 2 pcm. molar heat capacity. Using CORBA [8] or DCOM [9]. The function “Calculate” maps the input parameters (pressure. compression. 3. The false position method is combined with the successive bisection method to calculate the roots of the equation of state [4]. ∂Z ∂T = p R(T Z )2 C3 − p Z [T K 3 C0 + C4 ] . p I = j=1 y j cm. p is the molar heat capacity of the component j of the ideal gas mixture. The input/output parameters and functions are accessible. a j . temperature. which enables an easy integration into new software projects. and T is the temperature. pi = a j + b j j = T = T 2 −RTρm (Z ∂ρm ∂vm T + ρm C4 ) . Prior to the calculation of the molar heat capacities. (39) is given in [6] and [7]. while the internal structure is hidden from the user. The interface to the software object is shown in Fig. c j . 2. p ∂Z ∂T . isentropic exponent. pi (39) The derivation of the Eq. kn (31) (32) (33) k b Dn = (bn − cn kn ρr n )ρr n e−cn ρr . c. molar heat capacity. and Joule–Thomson coefﬁcient). cm. vm = Rρm [Z + T (C3 − ρr C0 )] (29) = p R p Z+ ∂Z ∂T T p (30) C3 = n=13 ∗ ∗ C n Dn . The molar heat capacities of the ideal gas mixture components can be approximated by the DIPPR/AIChE generic equations [5]. and e j are the corresponding constants. d. b j . the isentropic exponent. p cm. are deﬁned by the equations: ∂p ∂T and ∂vm ∂T where.96 752. kn (36) The isentropic exponent is deﬁned by the following relation cm. i. and the Joule–Thomson coefﬁcient is implemented in the OOP mode. compression. the density and the compression factor of a natural gas must be calculated.

. According to [2]. reduced density ρr = K 3 ρm and molar volume vm = 1/ρm . the expansibility factor ε for the oriﬁce plate with corner taps is deﬁned by: ε = 1 − (0. 4 Coefﬁcients Dn and D1n (Eqs. j . f n . i = 1. (14)) and temperature dependent coefﬁcients Cn (Eq.22 I. The corresponding temperature change T of the gas for the oriﬁce plate with corner taps is deﬁned by T = T1 − T2 ≈ µJT ( p1 . j = 1. but upstream temperature shall be used for the calculation of the ﬂow-rate.256β 4 + 0. and P is the pressure drop across the oriﬁce plate. p (Eq. it is generally assumed that the temperature drop across the differential device can be neglected. The above approximations may produce a measurement error. n = 1. (33)) 8 Partial derivatives of pressure: (∂ p/∂ T )vm (Eq. deﬁned by ω= 1 − β 4 1 − C 2 − Cβ 2 1 − β 4 1 − C 2 + Cβ 2 p (42) 4. ∗ Ui. u n . Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c Fig. (38)) 9 Ideal molar heat capacity of a gas mixture at constant pressure: cm. Table 3 The input/output parameters and the procedure for the computation of the natural gas properties Input parameters—constant: • Molar gas constant (R = 8314. which is related to the isentropic exponent. d j . The relative ﬂow measurement error Er is estimated by comparing the approximate (qm2 ) and the corrected (qm1 ) mass ﬂow-rate i. . 2. (25)) and ∗ Cn (Eq. gn . j .51 J/(kmol K)) • Natural gas equation of state parameters (an . Si .v (Eq. Within the limits of the application of ISO-5167 [2]. . p I (Eq. (27)) 10 Molar heat capacity of a gas mixture at constant volume: cm. T2 ) ω (41) where T1 and T2 indicate the corresponding temperatures upstream and downstream of the oriﬁce plate. . Interface to the software object that implements the calculation of the natural gas properties. (37)) 13 Joule–Thomson coefﬁcient µJT (Eq. qn . (43) . but it is also suggested that it be taken into account if higher accuracies are required. b j . i = 1. G i . G i.e. According to [10]. Application We investigated the combined effect of the Joule–Thomson coefﬁcient and the isentropic exponent of a natural gas on the accuracy of ﬂow-rate measurements based on differential devices. The ﬂow-rate through the oriﬁce is proportional to the expansibility factor. respectively. . . second virial coefﬁcient ∗ B (Eq. characterization parameters (Mi . 2. Wi . µJT ( p1 . . and ω is the pressure loss across the oriﬁce plate [11]. (24)) ∗ ∗ 6 1st and 2nd derivative of the coefﬁcient Cn : Cn (Eq. 1) is assumed to be completely in accordance with the international standard ISO-5167-2 [10]. 2. It is also assumed that the isentropic exponent can be approximated by the ratio of the speciﬁc heat capacity at constant pressure to the speciﬁc heat capacity at constant volume of the ideal gas. (26)) 7 1st derivative of the compression factor Z : (∂ Z /∂ T ) p (Eq. . wn . E i . (18)) 2 Compression factor Z (Eq. (23)) and B (Eq. the temperature of the ﬂuid shall preferably be measured downstream of the primary device. K i . while p1 and p2 are the absolute pressures upstream and downstream of the oriﬁce plate.351 + 0.93β 8 )[1 − ( p2 / p1 )1/κ ] (40) where β denotes the ratio of the diameter of the oriﬁce to the internal diameter of the pipe. 58). . The measurement of a natural gas [4] ﬂowing in a pipeline through an oriﬁce plate with corner taps (Fig. N) Input parameters—time varying: • Absolute pressure: p (MPa) • Absolute temperature: T (K) • Molar fractions of the natural gas mixture: yi . (39)) scheme is given in [2] and [10]. Fi . cn . (8)) (see ISO-12213-2 for details of calculation) 3 Molar density ρm = p/RT Z . (29)) and (∂ p/∂vm )T (Eq. . sn . Er = (qm2 − qm1 ) /qm1 . kn . T2 ) is the Joule–Thomson coefﬁcient at upstream pressure p1 and downstream temperature T2 . . (13)). K i. ∗ Q i . 21) and binary interaction parameters (E i. j . . . . e j . j ) (see ISO 12213-2) • DIPPR/AIChE gas heat capacity constants (a j . (32) and (36)) 5 1st and 2nd derivative of the second virial coefﬁcient B: B (Eq. bn . . . c j . (9)) 11 Molar heat capacity of a gas mixture at constant pressure: cm. (4)) 12 Isentropic exponent κ (Eq. 2. N Calculation procedure: 1 Mixture size parameter K (Eq. The detailed description of the ﬂowrate equation with the corresponding iterative computation where C denotes the coefﬁcient of discharge for the oriﬁce plate with corner taps [10].

08 J/(g ∗ K) of the measurement results for pressures up Fig.060 0.014 −0.043 0.064 −0.044 – 0.077 −0.025 – −0. Calculated and measured molar heat capacities at constant pressure of the natural gas mixture.029 – −0.075 −0.0 5. The procedure for the correction of the mass ﬂow-rate due to the adiabatic expansion effects is shown in Table 4.0 12. and 350 K).018 −0.012 Fig. 275.055 −0.113 0.026 −0.077 −0.031 −0.082 −0.042 – – – −0.0 250 275 300 (µJT calculated − µJT measured ) (K/MPa) −0. Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c Table 4 The procedure for the correction of the mass ﬂow-rate due to adiabatic expansion effects Step 1 Description Calculation of Joule–Thomson coefﬁcient µJT ( p1 .036 −0.030 – 0.0 2.002 −0. From Table 5.048 −0. .032 −0.0 25. T2 ) by using the procedure outlined in Table 3 with upstream pressure p1 and downstream temperature T2 Estimation of upstream temperature T1 using the Eq. are shown in Fig.0 3.0 2.023 −0.012 −0.I.0 11. The differences between the calculated values and the corresponding measurement results [13]. The calculation procedures are implemented in the OOP mode.075 −0.092 −0.082 – −0.050 0.5 10.0 3.059 0.5 20.032 – −0.041 −0.171 −0.012 −0.034 0.039 −0. The individual and the combined relative errors due to the approximations of the temperature drop and the isentropic exponent are calculated.5 10.194 2 3 4 5 Table 6 Difference between the calculated and measured Joule–Thomson coefﬁcient of a natural gas P (MPa): T (K) 0.032 −0.068 – −0.092 −0. The results of the measurements [13] and the results of the calculation of the speciﬁc heat capacities c p and the Joule–Thomson coefﬁcients µJT of the natural gas mixtures.79942. with the corresponding high accuracy measurement data [13] (Ernst et al.0 16.5 15.066 −0.009 0.023 −0.061 0. Measurement results In order to compare the calculation results.030 −0.070 350 −0.023 −0.033 −0. The results are presented in the following section.0 5.5 15.096 – 0.024 – −0.0 4.059 −0.025 −0.0 20. xCO2 = 0. Calculated and measured Joule–Thomson coefﬁcients of the natural gas mixture.098 – – −0.051 −0.043 0.134 −0.047 0.019 – 0.0 30.03000. for absolute pressures ranging from 0 to 30 MPa in 0.018 −0.016 −0.015 −0.033 −0. respectively. and xN2 = 0. xC2 H6 = 0.05029.069 −0. 3.026 – 0.022 0. 3 and Fig.002 0. respectively.093 0.033 – −0.048 – – – −0.075 −0.051 −0. 5. 4.022 −0.043 −0.0 7.0 17.069 – – −0.052 −0.081 −0.5 1.053 −0.036 – 0.0 25.02090.5 1.084 0.021 −0. are shown in Table 5 and Table 6.0 12.032 −0.020 −0.029 0. 4.025 0.0 30. for c p and µJT .020 −0.049 −0. we assume identical artiﬁcial natural gas mixtures with the following mole fractions: xCH4 = 0.0 7.022 −0. 300. for the speciﬁc heat capacity c p and the Joule–Thomson coefﬁcient µJT .09939.5 13.097 −0.011 −0.). xC3 H8 = 0.005 350 −0. it can be seen that the calculated values of c p are within ±0. (41) Calculation of density ρ = Mρm and isentropic exponent κ using the procedure outlined in Table 3 with upstream pressure p1 and estimated upstream temperature T1 Calculation of viscosity (residual viscosity function) [12] Calculation of mass ﬂow-rate in accordance with [10] 23 Table 5 Difference between the calculated and measured speciﬁc heat capacity at constant pressure of a natural gas P (MPa): T (K) 0.019 −0.027 −0.0 250 275 300 (c p calculated − c p measured ) (J/(g ∗ K)) −0.5 MPa steps and for four upstream temperatures (250.014 −0.

Temperature drop due to the Joule–Thomson effect T = µJT ω when measuring ﬂow-rate of the natural gas mixture through the oriﬁce plate with corner taps (ISO-5167-2). and n-pentane 0. the relative difference between the calculated and experimentally obtained c p never exceeds ±2. for absolute upstream pressures p1 ranging from 1 to 60 MPa in 1 MPa steps. but never exceeds ±0. Fig.00% and ±4. for absolute pressures p1 ranging from 1 to 60 MPa in 1 MPa steps. p (20 and 100 kPa). For pressures up to 12 MPa. downstream temperature T2 . Fig. The relative difference increases with the increase in pressure. viscosity. Calculated isentropic exponent of the natural gas mixture. Following the recommendations [2].0005. 7. 5. At higher pressures. The internal diameters of the oriﬁce and pipe are: d = 120 mm and D = 200 mm. of the primary device. The error is calculated in accordance with Eq. and for six equidistant upstream temperatures T1 in the range from 245 to 345 K.085. 1. a natural gas mixture (Gas 3) form Annex C of [4] is assumed to ﬂow through the oriﬁce plate with corner taps [9] shown in Fig. In order to simulate a ﬂow-rate measurement error caused by an inappropriate compensation for the adiabatic expansion.023. . ipentane 0. Fig. Fig. The approximate ﬂow-rate and the corresponding natural gas properties (density. propane 0. At higher pressures. carbon dioxide 0. it can be seen that the calculated values of µJT are within ±0. the relative difference may increase signiﬁcantly. Since the isentropic exponent is a theoretical parameter.24 I. and differential pressure p. 1) due to the Joule–Thomson effect is shown in Fig. The internal diameters of the oriﬁce and pipe are: d = 120 mm and D = 200 mm. 6 it can be seen that for each temperature there exists the corresponding pressure where the Joule–Thomson coefﬁcient changes its sign.015.0005. and isentropic exponent) are calculated at upstream pressure p1 .5% for pressures up to 12 MPa.113 K/MPa.2 J/(g ∗ K). The upstream pressure varies from 1 to 60 MPa in 1 MPa steps and upstream temperature from 245 to 305 K in 20 K steps for each of two differential pressures p (20 and 100 kPa). but never exceeds ±2. by neglecting the temperature drop due to the Joule–Thomson effect (T2 = T1 ).00%. The results of the calculations obtained for pure methane and methane–ethane mixtures are in considerably better agreement with the corresponding experimental data [13] than those for the natural gas mixture shown above. and downstream temperature from 245 to 305 K in 20 K steps for each of two differential pressures p (20 and 100 kPa). 6 illustrates the temperature drop due to the Joule–Thomson effect calculated in accordance with Eq. i-butane 0. (43) by comparing the approximate mass ﬂow-rate (qm2 ) with the corrected mass ﬂow-rate (qm1 ). Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c to 12 MPa. and the temperature downstream (T2 ).0035. 5 shows the results of the calculation of the isentropic exponent.0035. Fig.859. and consequently alters the sign of the temperature change. We estimate that the relative uncertainties of the calculated c p and µJT of the AGA-8 natural gas mixtures in common industrial operating conditions (pressure range 0–12 MPa and temperature range 250–350 K) are unlikely to exceed ±3. The upstream pressure varies from 1 to 60 MPa in 1 MPa steps. (41). From Fig. A relative error in the ﬂow-rate measurements (Fig. up to 30 MPa. 6.00%. ethane 0.010. nitrogen 0. with the experimental results for the pressures up to 30 MPa. when the values of µJT are close to zero. respectively. The results are shown for two discrete differential pressures p (20 and 100 kPa). The results calculated are given for two discrete differential pressures. n-butane 0. From Table 6. 7. the difference increases. and for four equidistant downstream temperatures T2 in the range from 245 to 305 K. Relative error Er = (qm2 − qm1 ) /qm1 in the ﬂow-rate of the natural gas mixture measured by the oriﬁce plate with corner taps (ISO-5167-2) when using downstream temperature with no compensation for the Joule–Thomson effect (qm2 ) instead of upstream temperature (qm1 ). The procedure for the precise correction of the mass ﬂowrate is shown in Table 4. A natural gas analysis in mole fractions is the following: methane 0. the absolute pressure is assumed to be measured upstream ( p1 ). there exist no experimental data for its veriﬁcation.

It would therefore seem sensible for the results of the Joule–Thomson and the isentropic exponent calculations to be used with caution above this pressure. 6. or subsequent operational changes in temperature. 7) and the isentropic exponent (Fig. and differential pressure p. which use natural gas fugacities to derive the molar heat capacities and are. The procedure for the precise correction of the mass ﬂow-rate is shown in Table 4. The error always increases by decreasing the operating temperature. The internal diameters of the oriﬁce and pipe are: d = 120 mm and D = 200 mm. p I /(cm. this usually takes the form of a ﬁxed value supplied by the user. Our further work will be directed towards the improvement of the model. could lead to signiﬁcant systematic metering errors. The approximate ﬂow-rate calculation is carried out in the same way. The upstream pressure varies from 1 to 60 MPa in 1 MPa steps and downstream temperature from 245 to 305 K in 20 K steps for each of two differential pressures p (20 and 100 kPa). The results are shown for two discrete differential pressures p (20 and 100 kPa). and up to 1. the . 9. therefore. The procedure for the precise correction of the mass ﬂow-rate is shown in Table 4.5% at lower operating temperatures (245 K). 8 illustrates the relative error in the ﬂow-rate measurements due to the approximation of the isentropic exponent by the ratio of the ideal molar heat capacities. The Fig. by neglecting the temperature drop due to the Joule–Thomson effect (T2 = T1 ) and by substituting the isentropic exponent with the ratio of the ideal molar heat capacities. p I − R). especially at lower temperatures and higher differential pressures. The internal diameters of the oriﬁce and pipe are: d = 120 mm and D = 200 mm. Fig. However. The upstream pressure varies from 1 to 60 MPa in 1 MPa steps. which lies within the wider ranges of application given in [4]. like natural gases with a high carbon dioxide content.I. and for four equidistant downstream temperatures T2 in the range from 245 to 305 K. Relative error Er = (qm2 − qm1 ) /qm1 in the ﬂow-rate of the natural gas mixture measured by an oriﬁce plate with corner taps (ISO-5167-2) when using downstream temperature. (43). with no compensation for the Joule–Thomson effect and the isentropic exponent of the ideal gas at downstream temperature (qm2 ) instead of upstream temperature. The measurement error is also dependent on the natural gas mixture. and the corresponding real gas isentropic exponent (qm1 ). (43). pressure or gas composition. p I − R)). The total measurement error is still considerable. 9 it can be seen that the maximum combined error is lower than the maximum individual errors. The calculations in this paper show that any initial error in choosing this value. for absolute upstream pressures p1 ranging from 1 to 60 MPa in 1 MPa steps. p I /(cm. The results are shown for two discrete differential pressures p (20 and 100 kPa). 9 shows the ﬂow-rate measurement error produced by the combined effect of the Joule–Thomson and the isentropic expansions. calculation results are shown up to a pressure of 60 MPa. Conclusion This paper describes the numerical procedure for the calculation of the natural gas molar heat capacity. because the Joule–Thomson coefﬁcient (Fig. and no uncertainty is quoted in Reference [4] for pressures above 30 MPa. 8. For certain mixtures. The results obtained for the Joule–Thomson coefﬁcient and isentropic exponent are in complete agreement with the results obtained when using the procedures described in [7] and [14]. and for four equidistant downstream temperatures T2 in the range from 245 to 305 K. downstream temperature T2 . κ = cm. the relative error in the ﬂow-rate may increase up to 0. which equals the ratio of the ideal molar heat capacities (κ = cm. with the aim of simplifying the calculation procedure and further decreasing the uncertainty of the calculation results. the lowest uncertainty for compressibility is for pressures up to 12 MPa. for absolute upstream pressures p1 ranging from 1 to 60 MPa in 1 MPa steps. Whilst modern ﬂow computers have a provision for applying a Joule–Thomson coefﬁcient and an isentropic exponent correction to measured temperatures. The error is calculated by comparing the approximate mass ﬂow-rate (qm2 ) with the corrected mass ﬂow-rate (qm1 ) in accordance with Eq. with the exception of the isentropic exponent.0% at very low operating temperatures (225 K). Fig. for each of two differential pressures p (20 and 100 kPa). and downstream temperature from 245 to 305 K in 20 K steps. of 0–65 MPa. 8) show the countereffects on the ﬂow-rate error. The error is calculated by comparing the approximate mass ﬂow-rate (qm2 ) with the corrected mass ﬂowrate (qm1 ) in accordance with Eq. and cannot be overlooked. considerably more computationally intensive and time consuming. From Fig. Relative error Er = (qm2 − qm1 ) /qm1 in the ﬂow-rate of the natural gas mixture measured by the oriﬁce plate with corner taps (ISO-5167-2) when using the isentropic exponent of the ideal gas (qm2 ) instead of the real gas (qm1 ). The approximate ﬂow-rate and the corresponding natural gas properties are calculated at upstream pressure p1 . Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c 25 Fig.

2005. ISO-51671-2. Joule–Thomson coefﬁcient and the isentropic exponent. Ref. 8. 1998. CORBA: Integrating diverse applications within distributed heterogeneous environments. The ﬂow measurement engineering book. White Paper. Microsoft Corporation.nuc. Ref. Ref. Flow calorimetric results for the massic heat capacity cp and Joule–Thomson coefﬁcient of CH4 . Calculation of natural gas isentropic c c exponent. Olander DR. Berkeley. Transmission measurement committee report no. [2] ISO-51671-1. of (0. Mari´ I. No. DIPPR R 801. Experiments in physical chemistry. ISO. ISO-51671-2:2003(E). ISO-51671-1:2003(E). Flow Measurement and Instrumentation 1997. from Department of Nuclear Engineering. Mari´ I. Sponsored by AIChE. and to Dr.edu/courses/classes/E-115/Reader/index. 2003. ISO-12213-2. 1992. New York: McGraw-Hill. Natural gas – calculation of compression factor – Part 2: Calculation using molar-composition analysis.26 I.16C2 H6 ). Urner G. 35(2):46–55. XQ 1285. University of California: Berkeley [Chapter 7]. The Joule–Thomson effect in natural gas ﬂow-rate measurements. Design Institute for Physical Properties.85CH4 + 0. Microsoft: DCOM Architecture. Journal of Chemical Thermodynamics 2001. The author would like to express his thanks to Professor Donald R. Pressure loss of oriﬁce plates according to ISO-5167. References [1] Shoemaker DP. Galovi´ A. Evaluated standard thermophysical property values. The corresponding equations have been derived by applying the fundamental thermodynamic relations to AGA-8 extended virial-type equations of state. Jaeschke M. Lemmon. USA. Measurement of ﬂuid ﬂow by means of pressure differential devices inserted in circular-cross section conduits running full — Part 2: Oriﬁce plates. NIST. ISO. Ernst G. c Flow Measurement and Instrumentation 2005.16(1):13–20. University of California. No. Nibler JW. 2003. and of a mixture similar to natural gas. IEEE Communications Magazine 1997. for his valuable suggestions. Mari´ / Flow Measurement and Instrumentation 18 (2007) 18–26 c General principles and requirements.8:39–41. Miller RW. Education. 3rd ed. ISO-122132:1997(E). Šmuc T. No. The implementation of the procedure in an OOP mode enables its easy integration into new software developments. Arlington (Va. 1996. for his help in obtaining the relevant measurement data. Wirbser H. AGA catalog no. USA. Acknowledgements [3] [4] [5] [6] [7] [8] This work has been supported by the Croatian Ministry of Science. WEB site: http://www. 6th ed.htm. Vinoski S. AGA 8. Olander. ISO. Keil B. Garland CW.berkeley.). Retrieved September 21. The DIPPR AIChE generic ideal heat capacity equations have been used to calculate the ideal molar heat capacities of a natural gas mixture. and Sport with the projects “Computational Intelligence Methods in Measurement Systems” and “Real-Life Data Measurement and Characterization”. Eric W. An example of a possible application of the procedure in the ﬂow-rate measurements has been given. Flow Measurement and Instrumentation 2005. New York: McGraw-Hill. In: Engineering thermodynamics. Measurement of ﬂuid ﬂow by means of pressure differential devices inserted in circular-cross section conduits running full — Part 2: [9] [10] [11] [12] [13] [14] . Thermodynamic relations.16:387–95. 2004. 1996. The procedure can be efﬁciently applied in both off-line calculations and real time measurements. 1997. Compressibility and supercompressibility for natural gas and other hydrocarbon gases.33:601–13.

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