All you’re going to learn today is:

PV = nRT and
PV = znRT

Gas Properties I
PETE 444

Sept. 6
 Overview
• Ideal Gas
– Equation of State
– Density of Ideal Gas
– Mixtures of Ideal Gas
– Some key parameters (which you will use a lot!)
• Real Gas
– Van der Waals
– Compressibility
– Law of corresponding states
2
 Ideal Gas
Defined
– volume occupied by gas molecules << total gas
volume.
– all molecular collisions are elastic.
– no attractive or repulsive forces among the
molecules.
p pressure, kPa
Gas Law Vm molar volume m3/mol,
V volume, m3
pVM R universal gas constant
=R
T 8.314 Pa-m3/mol-°K
VM n = V T temperature, °K
n no. of moles
pV = nRT
3
 Ideal Gas
Other useful variations
n = m/M m is mass, kg
M is molecular weight, kg/kg-mol
This gives pV=nRT=(m/M)RT

 = m/V  is density, kg/m3

This gives  =pM/RT

4
 Ideal Gas P-V Curve
 For 100 mol of ideal gas at 60 C,
0.3

0.25

0.2
V (m3)

0.15

0.1

0.05

0
0 5 10 15 20 25
P (MPa)
5
Craft & Hawkins, “Applied Petroleum Reservoir Engineering,” 1959. 6
 Example Problem 2.1
? Assume that methane is an ideal gas and
calculate the mass of methane gas
contained at 100 bar and 30 degree
Celsius in a cylinder with volume of 1 m3

7
 Example Problem 2.2
? Assume that methane is an ideal gas and
calculate the mass of methane gas
contained at 1000 psia and 80 F in a
cylinder with volume of 70 ft3

8
Dalton’s Law of Partial Pressure
 Consider a mixture of gas.
 Total pressure exerted by the mixture of gas is equal
to the sum of pressures exerted by its components
(law of additive pressures).
 Pressure exerted by each of components is known as
its partial pressure.
 The partial pressure of the components can be
calculated using the ideal gas law. Consider that the
gas mixture is ideal and contains three components.
RT RT RT
PA  nA , PB  nB , PC  nC
V V V
9
 Dalton’s Law of Partial Pressure
 According to Dalton, the total pressure P is the sum of
partial pressure:
P  PA  PB  PC

RT RT RT
P  nA  nB  nC
V V V

RT
P
V
n i i

10
 Dalton’s Law of Partial Pressure
 The ratio of pressure of the i-component, that is Pi, to total
pressure P is:
Pi ni ni
   yi
P  i ni n
where yi is the mole fraction of i-component in the gas
mixture. Therefore, the partial pressure of a component is
the product of its mole fraction times the total pressure of
the ideal mixture

Pi  yi P

11
Amagat’s Law of Partial Volume
 Amagat’s Law: Total volume occupied by an ideal
gas mixtures is equal to the sum of the volumes that
the pure components would occupy at the same
pressure and temperature.
 The volume occupied by the individual components
are known as the partial volumes.
RT RT RT
VA  n A , VB  nB , VC  nC
P P P
 Accordingly, the total volume V is the sum of partial
volumes,
V  VA  VB  VC
12
Amagat’s Law of Partial Volume
V  VA  VB  VC
RT RT RT
V  nA  nB  nC
P P P
RT
V
P
 n
i i

 The ratio of the partial volume of the component i,

that is Vi, to the total pressure P is
Vi ni RT / P ni
   yi
V nRT / P n
 So the volume fraction of the component i is equal to
the mole fraction of that component.
13
 Molecular Weight of a Gas Mixture
 A mixture of gas contains molecules of various sizes.
Often, we try to describe a gas mixture in terms of its
apparent molecular weight
M   i yi M i
• Example Problem 2.3
Given its approximate composition, determine the apparent
molecular weight of dry air
Component Mole fraction, yi Molecular weight
(g/mol)
Nitrogen 0.78 28.01
Oxygen 0.21 32.00
Argon 0.01 39.94 14
 Specific Gravity of Gases
 Specific gravity (γg) of a gas is the ratio of the density
of the gas to the density of dry air.
 g   g /  air
where the densities are measured at the same P and T
(normally STD).
 If we assume that both the gas and air obey the ideal
gas law, then the specific gravity can be written as:
PM g / RT Mg Mg Mg
g    
PM air / RT M air 28.97g/mol 29g/mol
where Mair is the apparent molecular weight of air and
Mg is the apparent molecular weight of gas 15
 Example Problem 2.4
? Let’s determine the specific gravity of a
typical gas mixture

Component Mole fraction, yi Molecular weight,

g/mol
Methane 0.94 16.04
Ethane 0.03 30.07
Propane 0.02 44.10
n-Butane 0.01 58.12

16
 Real Gases and the
Modern Equation of State
• Andrews
• van der Waals
• Amagat
• Gas deviation from ideal behavior
0.3

0.25

0.2
V (m3)

0.15

0.1

0.05

0
0 5 10 15 20 25
P (MPa)
17
 Thomas Andrews (1813-1885)
• Studied phase behavior
of CO2 (carbonic acid)
• Realized the continuity
between gas and liquid
phases
• 1869: accurately
identified conditions
where liquid and gas
properties were the same
(critical point)
• Presented phase data
(pressure vs. volume) as
“isotherms”
18
 Andrews’ Chart (Isotherms)
HIGH

Volume
(No Scale)

LOW Note that the critical point is defined around 75 atm,

31.1°C
Current value (GPSA) is 7374 kPa (72.8 atm), 304.11°K
(30.96°C)
PRESSURE, Atmospheres
19
 J.D. van der Waals (1837-1921)
• 1873: Ph.D. thesis described
a new equation to describe
non-ideal behaviour of gases
- the first modern equation of
state (EOS)
• 1880: wrote of a concept
called “corresponding
states”
• Continued work with binary
mixtures
• Recognized with Nobel Prize
in 1910
20
 van der Waals Equation
a
( p + 2 )(VM - b) = RT
VM
VM = V /n
an 2
( p + 2 )(V - bn) = nRT
V

a/v2 term corrects for forces

of attraction between
molecules
b corrects volume occupied
by molecules
Vm is molar volume (m3/mol)
n is no. of moles
21
Isotherms from VDW Equation
Isotherms for any pure substance can be calculated with
the van der Waals equation if the constants a and b are
known. It is useful to express these constants as function
of critical properties, i.e.

a = f(Tc, pc) and b = f(Tc,pc)

since Tc and pc can be measured experimentally. Then

substitute constants a and b into original VDW equation

a
(p + )(VM - b) = RT
VM2

and calculate P(v) or v(P)

22
 Isotherms from VDW Equation
Start with the VDW equation and then rearrange to obtain an
expression in pressure, p
a
( p  2 )(Vm  b)  RT
Vm
a RT
(p  ) 
Vm2 (Vm  b)
RT a
p  2
(Vm  b) Vm

Note that at the critical temperature

(Tc 31°C) the isotherm shows an
inflection at the critical point (pc, Vc), i.e.
p RTc

}
2a
0 
Vm c.p.  c  Vc
2 3 These two
V  b equations
2 p 2RTc 6a apply only at the
0  critical point!
Vm2 Vc  b
3
c.p.
Vc4
23
 Example Problem 2.5
? Prove that the parameter a and b in Van
der Waals EOS are given as

Tc and Pc are critical temperature and

pressure, respectively.

24
 Use of VDW EOS
Isotherms for CO2, can then be constructed using Van der
Waals’ EOS as follows:
1. Obtain critical values, Tc and pc
2. Calculate constants a, b
3. Select a range of values for molar volume, Vm
4. Calculate pressure, p, as a function of molar volume, Vm
and constant temperature, T
5. Plot p vs. Vm as family of curves for various
temperatures

From various references (McCain, GPSA) we find for CO2:

Tc = 304.1 °K (30.95°C) Andrews obtained very

pc = 7374 kPa similar values in 1869
25
 Calculate constants a, b.
Using the SI value, R = 8.314 kPa-m3/kmol-°K,
2
27 R T2
27 
2
kPa  m  3
1
a    304.1 K 
c 2
 8.314
64 pc 64  kmol  K  7374kPa
2 2
 m  3
1bar  m  3
a  365.7kPa     3.657bar  
 kmol  100 kPa  kmol 
and
RTc 1  kPa  m3   304.1 K 
b   8.314 
8 pc 8  kmol   K   7374kPa 
m3
b  0.0429 Let’s compare with values for a
kmol and b that have been calculated
by others…
26
 100 kPa = 1 bar

Moran & Shapiro, Fundamentals of Engineering Thermodynamics 27

 CO2 Isotherms from VDW Equation Isotherms for CO2
from Van der Waals Equation

1.0E+04
VDW at T=13°C
9.0E+03 VDW at T=21°C
VDW at T=31.1°C
8.0E+03 VDW at T=32.5°C
VDW at T=35.5°C
VDW at T=48°C
7.0E+03 NIST Data 31.1°C
Pressure, p [kPaa]

NIST Data 48°C

6.0E+03 Ideal Gas T=48°C

5.0E+03

4.0E+03

3.0E+03
RT a
2.0E+03 p= - 2
(Vm - b) Vm
1.0E+03
* NIST: National Institute of Standards and Technology
0.0E+00
0.0E+00 1.0E-01 2.0E-01 3.0E-01 4.0E-01 5.0E-01 6.0E-01 7.0E-01 8.0E-01

Molar Volume, Vm [m3/kmol]

28
 Corresponding States
Van der Waals later conceived of a universal form of his
equation of state by defining reduced values as follows:
p T V
pr = Tr = Vr =
pc Tc Vc

When substituted into his EOS, we have

æ aö
ç p + 2 ÷(V - b) = RT
è V ø
æ a ö
ç pr pc + 2 2 ÷(VrVc - b) = RTrTc
è Vr Vc ø

Recall that the constants a, b, and Vc were found to be

27 R 2Tc2 RT
a= b= c Vc = 3b
64 pc 8 pc
29
 Corresponding States
After some (?) derivations,
æ 3 ö 8Tr 3
ç pr + 2 ÷( 3Vr - 1) = 8Tr pr = - 2
è Vr ø 3Vr - 1 Vr

This remarkable equation suggests that in terms of

reduced parameters (Tr, pr, and Vr) the PVT relationship
of all pure substances is the same!

Let’s find out by using this new form of the VDW and
compare with modern data from NIST for CO2 and
ethylene (both well-studied in van der Waals’ time) at a
reduced temperature of Tr = 1.5 30
 Corresponding States
But first, it is also relatively simple to express the ideal
gas law in dimensionless form as follows:
pVm = RT pr = p / pc Vr = Vm /Vmc Tr = T /Tc
pr pcVrVmc = RTrTc
é RTc ù
prVr = Tr ê ú
ë pcVmc û

The presence of the term Vmc is inconvenient. We can

deal with it by restating the ideal gas law for the critical
point:
RTc
pcVmc = RTc Vmc =
pc
31
 Corresponding States
Substituting this into the dimensionless equation gives,
é RTc ù é RTc ù é pc ù
prVr = Tr ê ú = Tr ê úê ú
ë pcVmc û ë pc û ë RTc û
prVr = Tr

which turns out to be trivial.

We can include this equation with the others for

comparisons.

32
Corresponding States

33
 Corresponding States
• Observations on van der Waals
– The VDW EOS in terms of reduced parameters
provides a substantial improvement over the
ideal gas law
– The VDW EOS also provides a fair match with
actual behavior of some pure substances
– The p-v relationship for pure substances is quite
consistent when expressed in terms of reduced
parameters

34
 Other Famous EOS
Beattie Bridgeman (1927)

Benedict, Webb & Rubin (1940)

Redlich Kwong (1949)

Peng-Robinson (1976)

35
Deviations from Ideal Gas Behaviour
• Late 19th century work
• Early 20th century treatment
– Pure gases
– Natural gas mixtures

36
 Deviations from Ideal Gas
• Just one year before van der Waals, Emile Hilaire Amagat (1841-
1915) obtained his Ph.D. at University of Paris on the topic of
“Reserches sur la dilatation et la compressibilitie des gaz”
• Amagat spent the next 25 years on continued laboratory investigations
of gas compressibility.
• Studied various gases (air, oxygen, hydrogen, methane, nitrogen, CO2,
ethylene) over a wide range of temperatures and pressures, up to
40Mpa
– over 200 years earlier, Robert Boyle’s maximum pressure was about 400
kPa
• Observed that at high pressures, various gases did not obey the Boyle-
Mariotte relationship, pv=constant
• Proposed a factor, , as a measure of deviation of the product, pv, from
its value at a reference pressure (a not so convenient 24m Hg) and
volume, p´v ´ (isothermal):

37
 0.350

DEVIATION FROM IDEAL PV PRODUCT, 

PRESSURE, metres of Hg

Notes:
1. Reference state for p´v´ is at 24000mmHg.
2. All measurements taken at 15°C.

Annales de Chimie et de Physique, Vol. 5 No. 19, 1880

38
 Deviations from Ideal Gas
The US Bureau of Mines in 1916 and 1917 made
measurements of gas deviation (now called correction
factor) for pure gases and selected natural gases in the
US.

Aware that Amagat’s work was generally at high

pressures, the USBM extended the work down to 1 atm,
thus capturing a range of practical interest at the time -
gas networks were local operations.

Correction factors were tabulated for pure component

gases as well as selected natural gases.

39
 Deviations from Ideal Gas

Burrel and Robertson, “Compressibility of Natural Gas at High Pressures,” USBM Technical Paper No. 131, 1916 40
 Deviations from Ideal Gas
This method suffered from some flaws:
• correction factors for pure components were
made only at 15°C; no clear instruction was
given to adjust to actual gas temperature.
• the pure component correction factors were
simplified by assuming a linear relationship,
introducing error.
• pressures were limited to a maximum of 40
atm.

41
The Z-Factor

by definition, z = 1 for
an ideal gas

42
 Ideal gas: z=1 everywhere

pentane
propane
methane

at pr = 0, we are
effectively in a
vacuum

Brown, Souders and Smith in Industrial and Engineering Chemistry V24 N5, 1932. 43
 The Z-Factor of Mixtures
similar in form to Amagat’s charts,
While a single z-factor chart except p1V1 is now at std conditions
could be produced for pure
components using the reduced
values (Tr, pr), this was still not
possible for reservoir gas
mixtures, because they have a
more complicated notion of
critical pressure and
temperature.

Therefore, individual
laboratory analysis was
required for every gas mixture
or every reservoir gas! Kettleman Hills Field Gas Cap, California

Sage and Lacey in API Production Practice, 1936, 158-170. 44

 The Z-Factor of Mixtures

Methane-propane
mixtures

Sage, Lacey & Schaafsma, Ind. Eng. Chem, Vol. 26 No. 2, February, 1934, 214-217 45
 The Z-Factor of Mixtures
So, what do we do about Typical Phase Diagram of Gas Mixture
gas mixtures?
-Two component (binary) the REAL
-Multi component critical point

Does the concept of

corresponding states still
apply?

How are critical properties

defined? Can we use the
real critical point?

Some kind of “mixing

rule” might be required.

McCain, The Properties of Petroleum Fluids 46

 Next Lecture
• Gas Properties II
– Pseudo-critical properties
– Z-factor solutions
– Gas viscosity
• And some homework to help you learn

47
 Example Problem 2.1 (Solution)
Total quantity of methane in the cylinder

PVM
m  nM 
RT


100bar 10 Pa / bar 1m  16.04kg / kmol 
5 3

8314Pa  m / kmol  K  303.15K 

3

 63.64kg

Note:
30 o C   30  273.15  K=303.15K

48
 Example Problem 2.2 (Solution)
Total quantity of methane in the cylinder

PVM
m  nM 
RT


1000psia 70ft 3
16.04lb / lbmol 
 
10.73psia  ft 3 / lbmol  R 540 R 
 193.78lb
Note:
80 o F   80  460  o R=540 o R

49
 Example Problem 2.3 (Solution)
Molecular weight of air

M air   i yi M i

 0.78  28.01g/mol+0.21 32.00g/mol  0.01 39.94g/mol

  21.85  6.72  0.40  g/mol
 28.97g/mol  28.97kg/kmol=28.97lb/lbmol

We will use this value a LOT!

50
 Example Problem 2.4 (Solution)
First, get the molecular weight of gas mixture
M gas   i yi M i

  0.94 16.04+0.03  30.07  0.02  44.10  0.01 58.12  g/mol

 15.08  0.90  0.88  0.58  g/mol
=17.44g/mol

Then, obtain the specific gravity of gas mixture

M gas 17.44g/mol
g    0.601
M air 29g/mol

51
Example Problem 2.5 (Solution)
Rearrange to solve for the unknowns, a and b (note subscript c for
critical is assumed)
-RTc 2a 2a
3 ( c )
+ = = -
2
0 RT V b
(Vc - b)
c
2
Vc
3
Vc

6a (Vc - b)
3
-2RTc 6a
- 4 =0 RTc = 4
(Vc - b) Vc Vc
3
2

Now equate the two expressions for RTc from above, and simplify
2a (Vc - b) 6a (Vc - b)
2 2 2 3

= 4
Vc3
Vc 2
2a 2 (Vc - b) 6a 2 (Vc - b)
2 3
Vc3 Vc3
´ = 4 ´
Vc a(Vc - b) Vc a(Vc - b)
3 2 2
2
3a(Vc - b)
2a =
Vc 52
 Example Problem 2.5 (Solution)
Simplify some more:
2Vc = 3(Vc - b)
2Vc = 3Vc - 3b
Vc = 3b remember: at the critical pt only

Now, substitute into the first expression for RT

2a 2a 2a 8a
RTc = 3 (Vc - b) = 3 (
3b - b) = 4b =
2 2 2

Vc ( 3b) 27b 3
27b

Now put this expression for RT into the original VDW:

RTc a 8a 1 a
pc = - 2= - 2
(Vc - b) Vc 27b (Vc - b) Vc

53
 Example Problem 2.5 (Solution)
Continue to simplify:
8a 1 a
pc = - 2 Vc = 3b
27b (Vc - b) Vc
8a 1 a 8a 1 a 4a a 4a 3a
pc = - 2= - 2= - = -
27b (3b - b) 9b 27b (2b) 9b 27b 2 9b 2 27b 2 27b 2
a
pc =
27b 2
8 a
Now recall we found that RT c =
27 b
By rearranging the previous two equations to isolate a, we have
27
a = 27b pc = bRTc
2

8
RTc RTc
bpc = b= which is an extremely useful result.
8 8 pc
54
 Example Problem 2.5 (Solution)
8 a
Now returning to the equation RTc  27 b we substitute
the newly found expression for b to obtain,

8 a 
RTc 
27 b
27bRTc 27RTc RTc  27 R 2Tc2
a   
8 8 8 pc  64 pc

which can come in handy as well

55