CHAPTER 2

GASES

2.1 PRESSURE AND TEMPERATURE

PRESSURE

Pressure is force per unit area. The units used to express pressure are shown in Table 2.1.

The absolute pressure of a system is equal to the gauge pressure plus the ambient (surrounding)
atmospheric pressure.

Fig. 2.1 A simple apparatus used to

determine the pressure of a liquid.

Pa = Pg + PHg

where hliquide and hHg are the heights of the liquid and the mercury, respectively, in the column,
and dliquide and dHg are the densities of the liquid and the mercury, respectively.

Table 2.1. The units of pressure

Unit Definition Equal to Symbol

1 Newton/meter2
Pascal Pa
(N/m2 ou Kg/m.s2)
1.01325x105Nm2
The force exerted
or
by a column af
Atmosphere 1.01325dynes/cm2 Atm
mercury 760mm
760Torr
high/unit area
760mmHg
The pressure
exerted by 1mm
Torr 133.3224N/m2 Torr
column of mercury/
unit area
Pound/inch2 6894.7572N/m2 lb/in2 or
Bar 1x105N/m2 Psi
-6
Micron 1x10 torr u torr

The pressure-measuring devices that are used in laboratories are: the aneiroid barometer, the
precision-type bellows manometer, the Mcleod gauge, the diaphragm monometer, the capacitance
manometer and the ionization gauge. Some of these devices are used to measure low pressures.

TEMPERATURE

On the Celcius or centrigrade scale, the fixad value for the freezing point of water at 1 atm is
0ºC and that for the boiling point of water at 1 atm is 100°C.

T(ºK) = T(ºC) + 273 .15º

where T(º K) is the absolute Kelvin scale.

On the Fahrenheit scale, the fixed value for the freezing point of a satured NaCl - water is 0ºF ant
that for the boiling point of pure water is 212ºF.

T(ºF) = 9T/5(ºC) +32

2.2 LAWS OF IDEAL GASES

A gas that obeys the equation of stat PV = nRT is an ideal gas. All gases increasingly obey the
ideal gas law at increasingly law pressures; therefore, the equation PV=nRT is a limiting law for
the description of real gases.

Molecules of ideal gases occupy no volume and no interaction forces take place among them.

BOYLE'S LAW

Boyle's Law state that at constant temperature the volume of gas is inversely proportional to
the pressure:

V , or PV = constant
Fig 2.2 Applyng Boyle's law Fig. 2.3 Applyng Boyle's law

by plotting pressure as a by plotting pressure as a

unction of volume. function of the inverse of volume.

P1 V1 = P2 V2 (at constant temperature)

LAW OF GAY - LUSSAC AND CHARLES

The Law of Gay - Lussac states that at constant pressure, the volume of a gas is proportional to
its temperature, and that at constant volume, the pressure is proportional to its temperature:

V T (at constant P)
P T (at constant V)

= constant (at constant P)

(at constant V)

(at constant P)

PV = B (t + 273.15)

PV = BT

Fig. 2.4 PV as function of

temperature for different

quantities of gases.

T is the absolute temperature (ºK). t is the temperature in degrees Celsius (º).

AVOGADRO'S LAW

Avogadro's Law states that equal volumes of ideal gases contain equal numbers of molecules
under the same temperature and pressure conditions. The molar volume (Vm) is the volume
occupied by 1 mole of a gas.

COMBINED GAS LAW

= constant

PV = nRT

Where n is the number of moles of gas, and R is the gas constant.

DALTON'S LAW OF PARTIAL PRESSURES

Dalton's naw of partial pressures states that the total pressure of an ideal gas mixture is equal to
the sum of the pressures exerted by the individual gases (in the mixture) if placed in the same
vessel alone.
Ptotal = P1 + P2 + P3 + ... + Pn

Ptotal = Pj

where Pj is the partial pressure of component j in the mixture.

Pj = XjPtot

where Xj is the mole fraction of component j.

Ptotal =

P total = nj

Xj =

MOLECULAR WEIGHT OF AN IDEAL GAS

where m is the mass, and M is the molecular weight.

where d is the desnity.

2.2 REAL GASES

The deviations of real gases from ideality are caused by interactions between individual molecules.

The compressibility factor Z = measures the deviation from ideality. The amount that Z
deviates

from unity measures the lack of ideality in a real or imperfect or non - ideal gas.
Fig. 2.5 A plot of Z against pressure at low pressures.

The excluded volume (Vexcluded) is the volume that the gas molecules occupy because of their finite
size.

As the pressure increases, the relative error in negleting Vexcluded increases.

Volume of molecule =

Excluded volume per pair molecules =

Fig. 2.6 Excluded volume

THE VAN DER WAALS EQUATION

The Van der Waals equation of state is

Where b is the excluded volume of the molecules, and "a" is a constant. an2/ V2 is often called the
internal pressure of the gas.
The critical point is the pointof inflection. At this point the temperature is called the critical
temperature Tc , the pressure is called the critical pressure, Pc , and the volume is called the
critical volume Vc. The gas phase and the liquid phase are continuous at the critical temperature.
A liquid will not form above the critical temperature, regardless of how great the pressure is.

The reduced variables are the rations of the actual variables to the critical variables:

reduced pressure:
reduced temperature:

reduced volume :

The law of corresponding states proposes that real gases with the same values for any two of the
reduced variables will have the same values for the third variable.

The value of z is determined from the graph of zr plotted against Pr for different reduced
temperatures.

MOLECULAR WEIGHT OF A REAL GAS

For n moles of a real gas at low pressures

and

A low pressure, and

is the slope of the isothermal plot of d/P as a function of P, and is the intercept
of the same plot.

OTHER EQUATIONS OF STATE

The virtual equation

B(T) is the seconde virial coefficient, C(T) is the third virial coefficient, and so on.
where No is Avogadro's number, k is the Boltzmann constant, r is the distance between molecules,
and Vr is the intermolecular pair potential.