Chapter 5

Measurement of Gases
GAS VOLUMES
Gases, unlike liquids and solids, occupy volumes that depend very sensitively on pressure and temperature.
Special attention must therefore be given to factors influencing the volume of gases.

PRESSURE
Pressure is defined as the force acting normally on a unit area of surface.
Pressure =
Pressure (in pascals) =
force acting perpendicularly to an area
area over which the: force is distributed
force (in newtons)
area (in square meters)
Thus the pascal is defined by 1 Pa = 1 N/m2 = (1 kg . m/s2)/ni2 = 1 kg/m - s2.
The pressure exerted by a column of fluid is
Pressure = height x density of fluid x acceleration of gravity
Pressure (in Pa) = height (in m) x density (in kg/m3) x 9.81 m/s2
STANDARD ATMOSPHERIC PRESSURE
Air has weight and therefore exerts a pressure. The atmospheric pressure is due to the weight of the
overlying air. A standard atmosphere (1 atm) is defined as exactly 101 325 Pa. It is approximately equal
to the average pressure of the atmosphere at sea level. The standard atmosphere also is approximately
equal (within several parts in 107) to the pressure exerted by a column of mercury 760 mm high, at 0 "C
and at sea level. The torr is defined by: 760 torr= 1 atm. For problems in this book, the torr and the
millimeter of mercury (mmHg) will be taken to be the same. The bar is defined by: 1 bar=exactly 105 Pa.
One bar has recently replaced 1 atm as the standard pressure for reporting thermodynamic data.

PRESSURE GAGES
The pressure of a gas is frequently measured by attaching a manometer to the vessel. The manometer
contains a liquid, usually mercury, the height of which is readable in mm Hg (i.e. torr) pressure units. A
closed-tube manometer, Fig. 5-l(a), is originally filled all the way to the closed end, so that the difference
in mercury levels is the absolute value of the pressure of the gas. An open-tube manometer shows the
difference between the pressure in the gas and the barometric pressure. In Fig. 5-l(b) the gas pressure
is less than barometric, and in Fig. 5-l(c) it is more. A variety of other gages are used to measure
pressure. Those most commonly encountered are dial gages, which read relative pressure, that is the
pressure in exce:ss of barometric, analogous to the open tube manometer in Fig. 5-l(c). Absolute
gages (analogous to Fig. 5-l(a)) are usually so marked on them dial. Most gages used by motorists to check
their tires read the relative pressure.



STANDARD CONDITIONS (S.T.P.)
Standard conditions (S.T.P.) denotes a temperature of 0C (273.15 K, rounded off for most problems in
this book to 273 K) and normal atmospheric pressure (1 atm = 760 torr). As both the volume and density
of any gas are affected by changes of temperature and pressure, it is customary to reduce all gas volumes
to standard conditions for purposes of comparison.

GAS LAWS
At sufficiently low pressures and sufficiently high temperatures, all gases have been found to obey three
simple laws. These laws relate the volume of a gas to the pressure and temperature. When a gas obeys
these laws, it is said to behave as an ideal gas or perfect gas. These laws, which are described below, may
be applied only to gases which do not undergo a change in chemical complexity when the temperature or
pressure is varied. An example of a gas to which these laws do not apply is N02, which undergoes a
dimerization to N204 at increasing pressures or decreasing temperatures.

BOYLES LAW
When the temperature is kept constant, the volume of a given mass of an ideal gas varies inversely with the
pressure to which the gas is subjected. In mathematical terms, the product pressure x volume of a given
amount of gas remains constant. Thus, in comparing the properties of a given amount of an ideal gas under
two conditions, which we may call the initial andjinal states, we may write the following equation,
applicable at constant temperature:


A given subscript, 1 or 2, refers to a given state of the gas; 1 usually refers to an initial state and 2 to a final
state. This law furnishes the most direct test of how well a real gas corresponds to ideal behavior .

CHARLES LAW
At constant pressure, the volume of a given mass of gas varies directly with the absolute temperature.
Then, at constant pressure,



where Tl and T2 denote the absolute temperatures of the gas at the two states being compared.


GAY-LUSSACS LAW
At constant volume, the pressure of a given mass of gas varies directly with the absolute temperature.
Then, at constant volume,












COMBINED GAS LAW
Any two of the above three gas laws can be employed to derive a law which applies to all possiblem
combinations of changes:

for a fixed mass of gas. (See Problem 5.6.)
Since many gas calculations are concerned with determining a final volume given an initial volume, the
combined gas law is often written as

This expression indicates that the volume of a given mass of gas varies directly with the absolute
temperature and inversely with the pressure. Notice that, while T1 and T2 must be in kelvins, any
convenient absolute pressure unit may be used for PI and P2, and any convenient volume unit may be used
for V1 and V2.

DENSITY OF AN IDEAL GAS
As the volume of a given mass of gas increases, the mass per unit volume (i.e., the density) decreases
proportionately. Therefore the density ( d ) of a gas varies inversely with its volume. For an ideal gas, the
combined gas law then gives

DALTONS LAW OF PARTIAL PRESSURES
The partial pressure of a component of a gas mixture is the pressure which that component would exert if it
alone occupied the entire volume. According to Daltons law, the total pressure of a gaseous mixture is
equal to the sum of the partial pressures of the components. Daltons law is rigidly accurate only for ideal
gases. At pressures of only a few atmospheres or below, gas mixtures may be regarded as ideal gases, and
this law may be applied in calculations in this book.

COLLECTING GASES OVER A LIQUID
If a gas is collected over a volatile liquid, such as water, a correction is made for the amount of water vapor
present with the gas. A gas collected over water is saturated with water vapor, which occupies the total gas
volume and exerts a partial pressure. The partial pressure of the water vapor is a constant for each
temperature and is independent of the nature or pressure of the confined gas. This definite value of the
vapor pressure of water may be found tabulated as a function of temperature in handbooks or in other
reference books. If the total pressure (of the gas plus water vapor) is what is measured, the vapor pressure
must be subtracted from the total pressure in order to obtain the partial pressure of the gas. Pressure of gas
= (total pressure) - (vapor pressure of water) When a gas is collected over mercury, it is not necessary to
make a correction for the vapor pressure of mercury, which is negligible at ordinary temperatures.

DEVIATIONS FROM IDEAL BEHAVIOR
The laws discussed above are strictly valid only for ideal gases. The very fact that all gases can be
liquefied if they are compressed and cooled sufficiently is an indication that all gases become nonideal at
high pressures and low temperatures. The ideal properties are observed at low pressures and high
temperatures, conditions far removed from those of the liquid state. At pressures below a few atmospheres
practically all gases are sufficiently dilute for the application of the ideal gas laws with a reliability of a
few percent or better.