Chapter Two Properties of Gases

Chapter Two

Properties of Gases
Ideal Gas
It is an imaginary gas which obeys exactly certain simple laws such as the
laws of Boyle, Charles, Dalton and Amagat. No real gas obeys theses laws
exactly over all ranges of temperature and pressure, although the lighter gases
(hydrogen, Oxygen, air, ect.) under ordinary circumstances obey the ideal gas
laws but negligible deviations.

The properties of the heavier gases such as Sulfur dioxide and hydrocarbons,
particularly at high pressures and low temperatures deviate considerably from
those predicted by the ideal gas laws.

Vapors, under conditions near the boiling point, deviate markedly from the
ideal gas laws. However, at low pressures and high temperatures, the behavior
of vapor approaches that of an ideal gas.

Thus, for many engineering purposes the ideal gas laws if properly applied
will gave answers that are correct within a few percent or less. It is adequate
for many engineering calculations involving gases at low pressures.

The Ideal Gas equation of state (Perfect gas)

Equation of state relates the molar quantity and volume of gas to temperature
and pressure. From the work of Boyle and Charles, scientists developed the
relationship now called the Ideal Gas law:

𝑃𝑉=𝑍𝑛𝑅𝑇 (at low Pressure)

Where:

P = Absolute pressure of the gas. R = ideal gas constant.

V= Total volume occupied by the gas. T = absolute temperature of the Gas.
n = number of moles of the gas. Z= 1 for Ideal gas.
Z= Compressibility Factor for real gas (dimensionless)

1
Chapter Two Properties of Gases

Ideal Gas Constant:

Pressure (P) Volume (V) Mole (n) Temperature(T) Constant (R)

kPa m3 Kmole °K 8.314
bar m3 Kmole °K 0.08314
atm Liter Mole °K 0.08206
atm cm3 Mole °K 82.06

Stander conditions of Ideal gas

Each 1 mole of any gas occupies 22.4liter at 0°C and 1atm (STP).
System TS PS nS VS
SI 273K 1atm 1 mole 0.022415 m3
CGS 273K 1atm 1 mole 22.415 Lit

P . V / n . T = PS . VS / nS . TS

Example: Butane (C4H10) at 360°C and 3atm flows into a pipe at rate of
1100kg/hr, Molecular weight of Butane 58.1kg/kmol. Calculate the volumetric
flow rate of this stream by using:

1. Ideal gas law

2. standard conditions law

- at ideal gas law:

Basis:1hr T = 360+273 = 633°K

n = wt / M.wt =1100/58.1=18.93 kmol/hr =18.93*1000 mol

P. V=n.R. T

3*V=18.93*1000*0.08206*633=327816.2lit=327.8 m3

- at standard conditions law: ?

2
Chapter Two Properties of Gases

Ideal gas mixtures

A- Partial pressure of Dalton (Pi)

At constant volume at the same temperature of the mixture

𝑷𝒊 𝑽𝑻𝒐𝒕𝒂𝒍 = 𝒏𝒊 𝑹 𝑻𝑻𝒐𝒕𝒂𝒍

Pi is the partial pressure of component (i)

𝑷𝒊 = 𝒚𝒊 𝑷𝑻𝒐𝒕𝒂𝒍

yi = mole fraction of component (i)

PTotal = P1 + P2 + P3 + …………. + Pn

B- The partial volume of Amagat (Vi)

At constant pressure at the same temperature of the mixture

PTotal .Vi = ni .R.TTotal

Vi = yi VTotal

VTotal = V1 + V2 + V3 + ………… + Vn

Vol % = Mol%

Ex: A 3mol of (A) gas and 4mol of (B) gas are injected to each other, total
pressure and volume are 700 mmHg and 1.5 m3 respectively in the vessel. Find
the partial pressure and volume of each gas?

3
Chapter Two Properties of Gases

Real Gas (Non-Ideal Gas)

Several gases deviate from that predicted by the Ideal gas law as the pressure
increases or the temperature decreases. Thus, it is clear that we need some
way of computing the P-V-T properties of real gas.

Vander Waals Equation

Equation of state relate the P-V-T properties of a pure substance (or mixtures)
by theoretical or empirical relations:

𝑎 𝑛2
(𝑃 + 2 ) ( 𝑉 − 𝑛𝑏 ) = 𝑛 𝑅 𝑇
𝑉

𝑛𝑅𝑇 𝑎 𝑛2
𝑃= − 2
(𝑉−𝑛𝑏) 𝑉

Where:
a, b : are constants V = cm3
a = atm (cm3/mol)2 T = °K
b = cm3/mol n = mol
P = atm R = 82.06 atm. cm3/ mol. °K

Example: Nitrogen is desired to store 113.6 g in a cylinder having a volume of

21250 cm3 at temperature of 321.8°K. Calculate the pressure in atmospheres in
the cylinder by using Vander Waals equation:

a = 1.3478* 106 atm (cm3/mol)2, b = 38.6 cm3/mol, Mwt of N2 = 28 Kg/ Kmol

n=wt/M.wt=113.6/28=4.05mol
(P+(a. n2/V2)) *(V-n.b)=n.R.T

(P+(1.347*106*4.052/212502)) *(21250-(4.05*38.6)) =4.05*82.06*321.8

P=5.0289atm

For P= 3atm what the volume?

4
Chapter Two Properties of Gases

1. Average Molecular weight of gas (M.wt)

M.wt = ∑ atomic weight (kg/kmol)

M.wt = ∑ yi .Mwti

yi = mole fraction of comp. (i)

M.wt = y1 M.wt1 + y2 M.wt2 + y3 M.wt3+ ………. + yi M.wti

Example: Calculate the average molecular weight of air from its molar
composition of 79% N2, 21% O2? M.wt N2= 28kg/kmol, M.wt O2= 32 kg/kmol.

𝑀 . 𝑤𝑡 = 𝑦𝑁2 𝑀. 𝑤𝑡𝑁2 + 𝑦𝑂2 𝑀. 𝑤𝑡𝑂2

= 0.79*28+0.21*32

= 29 kg/kmol

2. Density of gas (ρ)

The density of gas is defined as the mass per unit volume.

ρ = P. M.wt / R. T

Unit of density is (kg/m3)

3. Specific gravity of gas (S.G)

Specific gravity is defined as the ratio of the density of the gas at a desired
temperature and pressure to that air (or any specified reference gas) at a
certain temperature and pressure.

S.G = Density of Substance / Density of reference

S.G = Density of Gas / Density of Air Specific gravity is dimensionless unit

Density of air = 1.29 kg/m3 at STP (STP = 101.325kN/m2, T = 273°K= 0°C)

ρ = P. M.wt / R T = 101.325*29 / 8.314*273 = 1.29 kg/m3

5
Chapter Two Properties of Gases

4. Molar volume (υ)

P°* υ° / T° = P * υ / T
υ (m3/kmol) = υ° * (T/T°) * (P°/P)

5. Specific volume of gas (ν)

ν=1/ρ
ν (m3/kg) = 22.4(m3/kmol) / M. wt (kg/kmol) * (T/T°) * (P°/P)

Example: Find the gas density, Specific Gravity and specific volume of Butane in
the previous example? On page no. (2)

ρ = P. M.wt / R T

= 3*58.1/0.08206*633=3.35kg/m3

S.G = Density of Gas / Density of Air

= 3.355/1.29=2.6

ν=1/ρ
= 1/3.35 = 0.298 m3/Kg

6. Heat Capacity of Gas

The Heat Capacity Cv and Cp are physical properties of materials. They may
be expressed in any units of energy per unit amount per unit temperature for
example J/ mol. °K. Heat capacities are functions of temperature:

Cp = a + b T + c T2 + d T3 a, b, c, d: are constants

For Ideal gas:

Cp = Cv + R

Cp mix = ∑ yi Cpi (T)

6
Chapter Two Properties of Gases

Generally

Cp of Mono atomic ideally (5/2 R) e.g He = 2.50 R

Cp of di atomic ideally (7/2 R) e.g H2 = 3.47 R

Cp of poly atomic ideally (8/2 R) e.g H2S = 4.11 R

These approximations break down from most large poly atomic molecular.
For example, ideally butane would have a molar heat capacity of 8/2R actually
it is Cp= 11.73. This is because polyatomic such as butane are not rigid bodies
but something between rigid bodies and a cloud of individual particles.

Example: Assuming Ideal gas behaviors calculate the heat that must be
transferred in each of the following:

1. A stream of Nitrogen flowing at a rate of 100mol/min is heated from 20°C

to 100°C (∆H).
2. Nitrogen contained in a 5liter flask at an initial pressure of 3 bar is cooled
from 90°C to 30°C (∆U).

Cp (N2) = 0.029+0.2199*10-5T+0.5723*10-8T2-2.871*10-12T3 (kJ/mol.C)

7
Chapter Two Properties of Gases

7. Vapor pressure of liquids (P*)

Many gases are used in liquid form either under pressure or at low temperature.
The liquid (or solid) form of a substance, if kept in a container with an ullage
space, will eventually reach a dynamic equilibrium with the gaseous form of that
substance. This equilibrium pressure, the saturated vapour pressure, is a
straightforward function of temperature only.

Normally when a liquid is heated gently molecules simply leave the liquid
surfaceVapor
for the gas phase
pressure and
refers to theevaporation is said between
equilibrium pressure to take the
place. If (or
liquid a liquid is gas
solid) and
heated phases
more vigorously bubbles
of a substance form in This
in a container. it when the depends
pressure saturatedsolely
vapour pressure When
on temperature.
a liquid is gently heated, molecules evaporate from the
of the liquid exceeds the gas pressure, the liquid is said to boil. surface. If heated more vigorously,
bubbles form when the vapor pressure exceeds the gas pressure, leading to boiling.
Conversely, condensation occurs during cooling. Vapor pressure can be calculated using
The converse process of condensation of the gas occurs during cooling and
empirical correlations.
can also take place either in the body of the gas or at a surface.

The equilibrium pressure is called the vapor pressure. Vapor pressure can be
calculated by some empirical correlations such as;
Vapor pressure is the pressure exerted by a vapor in
Antoine equation: equilibrium with its liquid or solid form at a given
temperature.
Antoine equation explains the change of vapor pressure with temperature.

Where:
P* = Vapor pressure (mmHg) or (kpa).
T = Temperature (°K) or (°C).
A, B and C = Constants.

Example: Calculate the vapor pressure of ethanol at 50°C?

A=18.5242, B=3578.91, C= 50.5

T (°K) = 50+273 = 323 °K

8
 Chapter Two Properties of Gases

ln P* = 5.390 P* = 221 mmHg

8. Diffusion of gas is the process through which gas molecules move from an area of
higher concentration to an area of lower concentration,
Diffusion refers to the net transport of material within a single phase in the absence
of mixing (by mechanicals means or by convection).

Both experiment and theory have shown that diffusion can result from pressure
gradients (pressure diffusion), temperature gradients (thermal diffusion), external
force fields (forced diffusion), and concentration gradients.

Only the last type is considered in this chapter; i.e., the discussion is limited to
diffusion in isothermal, isobaric systems with no external force field gradients.

1. Diffusion of gas (A) through a stagnant gas (B):

B mot Diffusion to A
=1
Diffusion of a-b
B Diffusion to A =
2
9
Chapter Two Properties of Gases

2. Equimolar counter diffusion: B Diffusion to A

NA = - NB
− 𝐷𝐴𝐵 (𝑃𝐴2 − 𝑃𝐴1 )
𝑁𝐴 =
𝑅𝑇 (𝑍2 − 𝑍1 )

Where:

NA= The rate of diffusion of gas (kmol/m2.s)

DAB = Diffusivity of gas (m2/s)
R= 8.314 kJ/kmol.°K
T= Temperature (°K)
P= Total Pressure (kN/m2)
PA1,PA2= Partial pressure of gas (kN/m2)
PB1,PB2 = Partial pressure of a stagnant gas (kN/m2)
PBM = (kN/m2)
(Z2-Z1) = X = Thick of stagnant layer (m)
PA2 = 0.0 (Stagnant gas)

a measure of how easily a substance diffuses through another medium

Diffusivity:
Diffusivity of gas (A) through gas (B) equal to diffusivity of gas (B) through gas
(A) in equimolar Counter diffusion, DAB = DBA
1 1 1⁄2
1 × 10−7 𝑇 1.75 ( + )
𝑀𝐴 𝑀𝐵
𝐷𝐴𝐵 =
1 1 2
𝑃 [(∑ υ𝐴 )3 + (∑ υ𝐵 )3 ]
νA= ∑νi

Where:

DAB = Diffusivity of gas (m2/s). P= Pressure (atm)

T= Temperature (°K) νA,νB = Molar volume of Mixture.
MA, MB= Molecular weight of gas νi = Atomic volume.
(kg/kmol).

10
Chapter Two Properties of Gases

D1 . P1 = D2 . P2
D1 = Diffusivity of gas at P1.
D2 = Diffusivity of the same gas at P2.

Example: Normal Butanol (C4H9OH) diffusing through air. Estimate the

diffusivity of normal Butanol in air:

- At temperature 0°C and 1 atm.

- At temperature 0°C and 2atm.
υc=16.5, υH=1.98, υO=5.49, υAir=20.1

1. T=0+273=273°K
M.wt (C4H9OH) =4*12+10*1+1*16=74 kg/kmol
M.wt Air = 29kg/kmol
∑υA(C4H9OH) =4*16.5+10*1.98+1*5.49=91.28
1 1 1⁄2
1 × 10−7 × 2731.75 ( + )
𝐷 = 74 29
𝐴𝐵 1 1 2
1× [(91.28)3 + (20.1)3 ]

= 7.73 × 10-6 m2/s

2- D1 . P1 = D2 . P2

7.73*10-6*1 = D2 * 2
D2= 3.865*10-6 m2/s

9. Viscosity of gas

If the local shear stress per unit area at any point is divided by the velocity
gradient, the ratio obtained is defined as the viscosity of the medium. Since
viscosity is defined as a shearing stress per unit area divided by a velocity
gradient, it should have the dimensions of (force).(time)/(length) 2 or mass/
(length).(time). Both dimensional groups are used, although for most scientific

11
Chapter Two Properties of Gases

work, viscosities are expressed in poises, centipoises, micropoises, etc. The

following conversion factors apply to viscosity units:

1P = 100 cP

= 1 g/(cm.s)

= 0.l N.s/m2

= 0.1 Pa.s

= 0.1 kg/m.S

kinematic viscosity is the ratio of the viscosity to the density. With viscosity
in poises (g/cm.s) and the density of grams per cubic centimeter (g/cm3), the
unit of kinematic viscosity is Stoke, with the unit square centimeters per
second (cm2/s). In the SI system of units, viscosities are expressed in N.s/m2
(or Pa.s) and kinematic viscosities in either (m2/s) or (cm2/s).

Estimation of low-pressure gas viscosity

Corresponding states methods

The specific form suggested by Lucas is illustrated below:

Where:

η= Viscosity (µP)
Ɛ= Reduced inverse Viscosity (µP)-1
Tr= Reduced Temperature (°K) TR=T/TC
𝐹𝑃° , 𝐹𝑄° , = Correction factors to account for polarity or quantum effects
𝐹𝑃° , = Reduced Dipole moment (Debyes)

TC= Critical Temperature (°K)

12
Chapter Two Properties of Gases

PC= Critical Pressure (bar)

M.wt= Molecular Weight (Kg/Kmol)

𝑭°𝑸 = 𝟏. 𝟐𝟐𝑸𝟎.𝟏𝟓 {𝟏 + 𝟎. 𝟎𝟎𝟑𝟖𝟓 [(𝑻𝒓 − 𝟏𝟐)𝟐 ]𝟏⁄𝑴 𝒔𝒊𝒈𝒏 (𝑻𝒓 − 𝟏𝟐)}

Q = 1.38 (He) , Q = 0.76 (H2) , Q = 0.52 (D2)

Sign (+1 or -1) depending on the values of the argument ( ) is greater

than or less than Zero.

𝐹𝑃° values are found as:

Where:
µr= dimensionless Dipole moment
µ= Dipole moment (Debyes)
TC=Critical Temperature (°K)
PC= Critical Pressure (bar)

Example: Estimate the viscosity of Methanol Vapor at a temperature of

550K and 1 bar by using Lucas method.
Where:
TC=512.64K, PC= 80.97 bar, ZC= 0.224, M.wt= 32.042 and µ=1.7 Debyes

13
Chapter Two Properties of Gases

Viscosity of Gases Mixture

𝒏
𝒚𝒊 × 𝜼𝒊
𝜼𝒎 = ∑ 𝒏
∑ 𝒚𝒋 × ∅𝒊𝒋
𝒊=𝟏 𝒋=𝟏

𝟏 𝟏 𝟐
𝜼𝒊 𝟐 𝑴. 𝒘𝒕𝒋 𝟒
[𝟏 + (𝜼 ) (𝑴. 𝒘𝒕 ) ]
𝒋 𝒊
∅𝒊𝒋 = 𝟏
𝑴. 𝒘𝒕 𝟐
[𝟖 (𝟏 + 𝑴. 𝒘𝒕𝒊 )]
𝒋

𝜼𝒋 𝑴. 𝒘𝒕𝒊
∅𝒋𝒊 = ( ) ( ) ∅𝒊𝒋
𝜼𝒊 𝑴. 𝒘𝒕𝒋

Example: Viscosity of pure Methane and n- Butane are 109.4 and 72.74µP
when the mole fraction of n-Butane is 0.303 at 293°K. Estimate viscosity of
gas mixture. M.wt CH4 = 16.043, M.wt C4H10= 58.123

14
Chapter Two Properties of Gases

10.Thermal conductivity of gas

Thermal conductivities of gases are considered in this matter. The units used
for thermal conductivity are W/ (m.K).

1 BTU = 252 Cal

1 Cal = 4.184 J

Thermal Conductivities of Polyatomic Gases:

Thermal Conductivities For non-polar gases, Stiel and Thodos (1964)

suggested:

Where:
λ = Thermal conductivity W/ (m.K)
η = Viscosity N.S/ m2 (1 Poise = 0.1 N.S/ m2)
Cp = Heat Capacity J/mol.K
M.wt = Molecular weight Kg/mol
R = Gases Constant 8.314 J/mol.K.

Eucken 's equation

Approximate values for the thermal conductivity of pure gases up to moderate

pressures can be estimated from values of the gas viscosity using Eucken 's
equation(1911):

Where:
η = Viscosity mN.s/m2. ( 1N = 1000mN)
Cp = Specific heat Capacity KJ/Kg.C.
M.wt = Molecular weight (kg/kmol).

15
Chapter Two Properties of Gases

Example: Estimate the thermal conductivity of ethane at 1 bar and 450°C. Cp=
2.47kJ/kg.C, η= 0.0134mN.s/m2 , Mwt= 30kg/kmol.

= 0.38 W/m.°C

Thermal Conductivities of Low Pressure Gas Mixtures

Wassiljewa Equation

In a form analogous to the theoretical relation for mixture viscosity

Where:
λm = thermal conductivity of the gas mixture.
λj = thermal conductivity of pure i.
yi , yj = mole fraction of components i and j.

This empirical relation was proposed by Wassiljewa (1904).

Mason and Saxena Modification

The relation for estimating mixture viscosities is also applicable to thermal

conductivities by simply substituting λ for η.
2
𝜂𝑖 1⁄2 𝑀. 𝑤𝑡𝑖 1⁄4
𝜀 [1 + ( ) (𝑀. 𝑤𝑡 ) ]
𝜂𝑗 𝑗
𝐴𝑖𝑗 =
𝑀. 𝑤𝑡 1⁄2
[8 (1 + 𝑀. 𝑤𝑡𝑖 )]
𝑗

16
Chapter Two Properties of Gases

𝐴𝑖𝑗 𝜂𝑖 𝑀. 𝑤𝑡𝑗
= ×
𝐴𝑗𝑖 𝜂𝑗 𝑀. 𝑤𝑡𝑖
ɸij = AIJ , ɸji = Aji

Mason and Saxena proposed a value of 1.065 for Ɛ, and Tandon and Saxena
(1965) later suggested 0.85. As used here, Ɛ= 1.0.
Ɛ = numerical constant near unity

Example: Estimate the thermal conductivity of a gas mixture containing 25

mole % benzene and 75 mole % argon at 100.6 °C and about 1 bar. The
experimental value is 0.0192 W/ (m. K) (Bennett and Vines, 1955).

17
Chapter Two Properties of Gases

A. Effect of Temperature on the Thermal Conductivities of Low

Pressure Gases
Thermal conductivities of low-pressure gases increase with temperature.
Generally, dλ/dT ranges from 4 *10-5 to 1.2 *10-4 W/(m. K), with the
more complex and polar molecules having the larger values.

B. Effect of Pressure on the Thermal Conductivities of Gases

The thermal conductivities of all gases increase with pressure, although

the effect is relatively small at low and moderate pressures.

Very Low Pressure

Below pressures of about 10-3 bar, the mean free path of the molecules is
large compared to typical dimensions of a measuring cell, and there is
almost proportional to pressure.

Low Pressure

This region extends from approximately 10-3 to 10 bar. The thermal

conductivity increases about 1% or less per bar.

High Pressure

Increasing temperature at low pressures results in a larger thermal

conductivity, but at high pressure the opposite effect is noted. Pressure
effects (except at very high pressures) are small below TC.

18