Chapter 2

2.1 Some Basic Definitions

• The system: a particular part of the universe in

which we are interested.
 Some Basic Definitions
• An open system is one that can exchange both
mass and energy with its surroundings.
• A closed system is one that does not exchange
mass with its surroundings but can exchange
energy.
• An isolated system is one that can exchange
neither mass nor energy with its surroundings
• See Figure 2.1
 Some Basic Definitions
• Most of the properties of matter may be divided
into two classes: extensive properties and
intensive properties.
• Properties whose values are directly
proportional to the amount of the material
present in the system are called extensive
properties: mass, area, volume, energy
• Those that do not depend on the amount are
called intensive properties: temperature, density
 Some Basic Definitions
• 2.2 An Operational Definition of Temperature

• Zeroth Law of Thermodynamics: If two

systems are in thermal equilibrium with the
third, they must also be in thermal equilibrium
with each other.
 Some Basic Definitions
• Isotherm: a curve that has a locus of points
which represent all of the same temperature

• See Figure 2.2

 Figure 2.2:

Plot of pressure (P) versus volume (V) at constant temperature for a given amount of a gas. Such a graph is called an isotherm .
 Some Basic Definitions
• 2.3 Boyle’s Law

• The volume (V) of a given amount of gas at

constant temperature is inversely proportional
to its pressure (P).

• (2.1) PV = constant or P1V1 =P2V2

 Some Basic Definitions
• Boyle’s Law at constant number of moles (n)
and Temperature (T):

• P1V1 = P2V2
 Some Basic Definitions
• 2.4 Charles’ and Gay – Lussac’s Law

• At constant pressure, the volume of a gas

sample expands when heated and contracts
when cooled.
 Figure 2.3:
Plots of the volume (V) of a given amount of gas versus temperature (?) at different
pressures. All gases ultimately condense if they are cooled to low enough
temperatures. When these lines are extrapolated, they all converge at the point
representing zero volume and a temperature of —273.15 °C.
 Some Basic Definitions
• William Thomson (Lord Kelvin, 1824-1907)
identified —273.15 °C as absolute zero, which
is theoretically the lowest attainable
temperature.
• On the kelvin scale, one kelvin (K) is equal in
magnitude to one degree Celsius.
• T/K = t/oC + 273.15
 Some Basic Definitions
• By convention, we use T to denote absolute
(kelvin) temperature and t to indicate
temperature on the Celsius scale.

• Absolute temperatures must be used in gas

law problems and thermodynamic
calculations.
 Some Basic Definitions
• Charles' law, or the law of Charles and Gay-
Lussac: V α T

• An alternative form of Charles' law relates the

pressure of a given amount of gas to its
temperature at constant volume:

• P α T or P/T = constant
 Some Basic Definitions
• To relate the volume/temperature and
pressure/temperature values of a gas in states
1 and 2:
• V1/T1 = V2/T2 (constant n and P)

• P1/T1 = P2/T2 (constant n and V)

 Some Basic Definitions
• 2.5 Avogadro’s Law
• He proposed that equal volumes of gases at
the same temperature and pressure contain
the same number of molecules.

• V α n or V/n = constant (constant T and P)

 Some Basic Definitions
• 2.6 The Ideal-Gas Equation

• Combining Avogadro’s, Boyle’s and Charles’

laws:
• V α nT/P
• V = RnT/P or PV = nRT
• R: proportionality constant for 1 mole of gas
 Some Basic Definitions
• Experimentally, it is found that 1 mole of an
ideal gas occupies 22.414 L at 1 atm and
273.15 K (a condition known as standard
temperature and pressure, or STP).

• R = (1 atm) (22.414L) / (1 mole) (273.15 K)

• R = 0.08206 L atm / K mol

 Some Basic Definitions
• To express R in units of J K-1 mol-1, we use the
conversion factors:

• 1 atm= 1.01325 x 105 Pa

• 1 L= 1 x 10-3 m3

• 1Pa = 1N m-2
Some Basic Definitions
 Some Basic Definitions
• From the two values of R, we can write:
• 0.08206 L atm K-1 mol-1 = 8.314 J K-1 mol-1
• or
• 1 L atm= 101.3 J
• and
• 1 J = 9.87 x 10-3 L atm
 Example 2.1
• Air entering the lungs ends up in tiny sacs
called alveoli, from which oxygen diffuses into
the blood. The average radius of the alveoli is
0.0050 cm, and the air inside contains 14 mole
percent oxygen. Assuming that the pressure in
the alveoli is 1.0 atm and the temperature is
37 °C, calculate the number of oxygen
molecules in one of the alveoli.
Answer to Example 2.1
Answer to Example 2.1 (con’t.)
Answer to Example 2.1 (con’t.)
2.7 Dalton’s Law of Partial Pressures
 Dalton’s Law of Partial Pressures
• where P1, P2,... are the individual or partial
pressures of components 1,2,...

• Σ is the summation sign

Dalton’s Law of Partial Pressures
Dalton’s Law of Partial Pressures
Dalton’s Law of Partial Pressures
• where x1 and x2 are the mole fractions of gases
1 and 2.

• A mole fraction, defined as the ratio of the

number of moles of one gas to the total
number of moles of all gases present, is a
dimensionless quantity.
Furthermore, by definition, the sum of all
the mole fractions in a mixture must be
unity, that is
 Dalton’s Law of Partial Pressures
• To obtain partial pressures, we need to know
the mole fractions of the components.
• A mass spectrometer can be used to
determine partial pressures.
• The relative intensities of the peaks in a mass
spectrum are directly proportional to the
amounts, and hence to the mole fractions, of
the gases present.
 Example 2.2
• The oxygen gas generated in an in vitro
photosynthesis experiment (conducted by
shining visible light on extracted chloroplasts)
is collected over water. The volume of the gas
collected at 22.0 °C and an atmospheric
pressure of 758.0 torr is 186 mL. Calculate the
mass of oxygen obtained. The vapor pressure
of water at 22.0 °C is 19.8 torr.
 Answer to Example 2.2
• Our first step is to calculate the partial
pressure of oxygen. According to Dalton's law,
the total pressure is equal to the sum of the
pressures of oxygen gas and water vapor, so
we write
• PT = PO2 + PH2O or
• PO2 = PT - PH2O
• = (758.0 - 19.8) torr = 738.2 torr = 0.971 atm
 Answer to Example 2.2 (con’t.)
• From Equation 2.8 we write: PV = nRT
• PV = (m / M )RT
• where m and M are the mass of 02 collected and the
molar mass of 02, respectively. Thus,
•
m = PV M / RT
•
m = (0.971 atm)(0.186 L)(32.00 g mol-1)
(0.08206 L atm K-1 mol-1)(295 K)
• m = 0.239 g
 2.8 Real Gases
• The ideal-gas equation holds only for gases that
have the following properties: (1) the gas
molecules possess negligible volume, and (2)
there is no interaction, attractive or repulsive,
among the molecules.
• Obviously, no such gases exist.
• Nevertheless, the ideal-gas equation is quite
useful for many gases at high temperatures or
moderately low pressures (< 10 atm).
 Real Gases
• One way to measure the deviation from
ideality is to plot the compressibility factor (Z)
of a gas versus pressure.
• Starting with the ideal-gas equation, we write:
• PV = nRT
• Z = PV/nRT
• Z = PVm / RT with Vm is molar volume
 Real Gases
• For an ideal gas, Z = 1 for any value of P at a
given T.
• However, as Figure 2.4 shows, the
compressibility factors for real gases exhibit
fairly divergent dependence on pressure.
Figure 2.4
 Real Gases
• At low pressures, the compressibility factors of
most gases are close to unity.
• In fact, in the limit of P approaching zero, we
have Z = 1 for all gases.
• This finding is expected because all real gases
behave ideally at low pressures.
 Real Gases
• As pressure increases, some gases have Z < 1,
which means that they are easier to compress
than an ideal gas.
• Then, as pressure increases further, all gases
have Z > 1.
• Over this region, the gases are harder to
compress than an ideal gas.
• These behaviors are consistent with our
understanding of intermolecular forces.
 Real Gases
• In general, attractive forces are long-range
forces, whereas repulsive forces operate only
within a short range.
• When molecules are far apart (for example, at
low pressures), the predominant intermolecular
interaction is attraction.
• As the distance of separation between
molecules decreases, the repulsive interaction
among molecules becomes more significant.
 The van der Waals Equation
• The van der Waals equation of state attempts
to account for the finite volume of individual
molecules in a nonideal gas and the attractive
forces between them.
The van der Waals Equation
 Figure 2.5
Effect of intermolecular forces on the pressure exerted
by a gas.
 Figure 2.5 (con’t.)
Effect of intermolecular forces on the pressure exerted
by a gas.
The speed of a molecule that is moving toward the
container wall (red sphere) is reduced by the
attractive forces exerted by its neighbors (gray
spheres).
Consequently, the impact this molecule makes with the
wall is not as great as it would be if no
intermolecular forces were present.
In general, the measured gas pressure is lower than the
pressure the gas would exert if it behaved ideally.
 The van der Waals Equation
• The reduction in pressure depends on the
number of molecules present or the density of
the gas, n/V

• Reduction in pressure due to attractive forces

α (n/V)(n/V)
= a(n2/V2) with “a” being the proportionality
constant
 Equation 2.11
• P is the measured pressure of the gas and
• (P + an2/V2) would be the pressure of the gas if
there were no intermolecular forces present.
• To allow for the finite volume of molecules,
we replace V in the ideal-gas equation with
(V - nb), where nb represents the total
effective volume of n moles of the gas.
 The van der Waals Equation
• The value of a is related to the magnitude of
attractive forces.
• The value of a corrects for intermolecular
attraction which makes pressure less than ideal.
• The quantity b is proportional to the size of the
molecule.
• The quantity b is close to the molar volume of
liquid and is a measure of molecular size.
 The van der Waals Equation
• The van der Waals equation is valid over a
wider range of pressure and temperature than
is the ideal-gas equation.
• Furthermore, it provides a molecular
interpretation for the equation of state.
• At very high pressures and low temperatures,
the van der Waals equation also becomes
unreliable.
 Example 2.3
• To synthesize ammonia using the Haber
process, 2000 moles of nitrogen (N2) are
heated in an 800-L vessel to 625 °C. Calculate
the pressure of the gas if N2 behaves (a) as a
van der Waals gas and (b) as an ideal gas.
 Answer to Exercise 2.3
• (a) Equation (2.11) can be rearranged as follows: P
= nRT - an2
V – nb V2
Using the van der Waals constants for nitrogen in
Table 2.1, we write:
P = (2000 mol)(0.08206 L atm / K mol)(898 K)
800 L – (2000 mol x 0.0386 L / mol)
- (1.35 atm L2 /mol2)(2000mol)2

(800L)2
P = 195 atm
 Answer to Exercise 2.3 (con’t.)
• (b) For an ideal gas, Equation 2.8 becomes:
• P = nRT/V
• P = (2000mol)(0.08206 L atm /mol K)(898 K)
(800 L)
P = 184 atm
The Virial Equation of State
 The Virial Equation of State
• In this relationship, the compressibility factor is
expressed as a series expansion in inverse powers
of molar volume V:
• B, C, D, are called the second, third, fourth,...
virial coefficients.
• An alternate form of the virial equation is given
by a series expansion of the compressibility
factor in terms of the pressure, P:
Alternate Form of ViriaI equation
Comparison of VDW and Virial Equations

• The van der Waals equation accounts for the

nonideality of gases by correcting for the finite
molecular volume and intermolecular forces.
• These corrections do result in a definite improvement
over the ideal gas equation.
• However, Equation 2.11 is still an approximate
equation.
• On the other hand, Equation 2.12 is accurate for real
gases, but it does not provide us with any direct
molecular interpretation.
 Example 2.4
• Calculate the molar volume of methane at 300
K and 100 atm, given that the second virial
coefficient (B) of methane is —0.042 L mol-1.
Compare your result with that obtained using
the ideal-gas equation.
Answer to Example 2.4
Answer to Example 2.4 (con’t.)
Answer to Example 2.4 (con’t.)
Answer to Example 2.4 (con’t.)
 2.9 Condensation of Gases and the Critical
State
• Thomas Andrews (1813-1885) measured the
volume of a given amount of carbon dioxide
as a function of pressure at various
temperatures.
• He obtained a series of isotherms like those
shown in Figure 2.6.
 Figure 2.6
Isotherms of carbon dioxide at various temperatures
(temperature increases from T1 to T7).
 Figure 2.6 (con’t.)
• The critical temperature is T5.
• Above this temperature, carbon dioxide
cannot be liquefied no matter how great the
pressure.
• At high temperatures, the curves are roughly
hyperbolic, indicating that the gas obeys
Boyle's law.
 Figure 2.6 (con’t.)

• As the temperature is lowered, deviations

become evident, and a drastically different
behavior is observed at T4.
• Moving along the isotherm from right to left, we
see that the volume of the gas decreases with
pressure.
• However, the product PV is no longer a constant
(because the curve is no longer a hyperbola).
 Figure 2.6 (con’t.)
• Increasing the pressure further, we reach a point
that is the intersection between the isotherm and
the dashed curve on the right.
• If we could observe this process, we would note
the formation of liquid carbon dioxide at this
pressure.
• With the pressure held constant, the volume
continues to decrease (as more vapor is converted
to liquid) until all the vapor has been condensed.
 Figure 2.6 (con’t.)
• Beyond this point (the intersection between
the horizontal line and the dashed curve on
the left), the system is entirely liquid.
• Any further increase in pressure will result in
only a very small decrease in volume.
• This is due to the fact that liquids are much
less compressible than gases (Figure 2.7).
 Figure 2.6 (con’t.)
• The pressure corresponding to the horizontal line (the
region in which vapor and liquid coexist) is called the
equilibrium vapor pressure or simply the vapor pressure
of the liquid at the temperature of the experiment.
• The length of the horizontal line decreases with
increasing temperature.
• At a particular temperature (T5 in this case), the
isotherm is tangential to the dashed curve and only one
phase (the gas phase) is present. The horizontal line is
now at a point known as the critical point.
 Figure 2.6 (con’t.)
• The critical temperature is the temperature
above which no condensation can occur no
matter how great the pressure.
• The critical constants of several gases are listed
in Table 2.2.
• Note that the critical volume is usually expressed
as a molar quantity, called the molar critical
volume (Vc), given by Vc/n, where n is the
number of moles of the substance present.
 Figure 2.7
The liquefaction of carbon dioxide at T1 (see Figure 2.6).
 Figure 2.7 (con’t.)
• In part (a), the first drop of the liquid appears.
• From parts (b) to (c), the gas is gradually and
completely converted to liquid at constant
pressure.
• Beyond part (c), the volume decreases only
slightly with increasing pressure because liquids
are highly incompressible.
• Part (d) shows an overall plot of the stages
shown in (a), (b), and (c).
Table 2.2
Condensation of Gases and the Critical State

• The phenomenon of condensation and the

existence of a critical temperature are direct
consequences of the nonideal behavior of gases.
• The force among molecules is attractive when
they are relatively far apart.
• As they get closer to one another (for example,
a liquid under pressure) this force becomes
repulsive, because of electrostatic repulsions
between nuclei and between electrons.
• At temperatures below Tc, it is possible to
compress the gas and bring the molecules
within this attractive range, where
condensation will occur.
• Above Tc, the kinetic energy of the gas
molecules is such that they will always be able
to break away from this attraction and no
condensation can take place.
The van der Waals constants a and b and the
critical constants.
The van der Waals constants a and b and the
critical constants.
• If the critical constants of a substance are
known, we can calculate both a and b.
• Rearranging the above three equations gives
equations 2.24 and 2.25.
• These are frequently used to obtain van der
Waals constants.
Van der Waals constants
 Figure 2.8
The critical phenomenon of sulfur hexafluoride
(Tc = 318.7 K; Pc = 37.6 atm).
 Figure 2.8 (con’t.)
• (a) Below the critical temperature, a clear
liquid phase is visible.
• (b) Above the critical temperature, the liquid
phase disappears.
• (c) The substance is cooled just below its
critical temperature.
• (d) Finally, the liquid phase reappears.