Physical Chemistry

Chap 1. The properties of gases

Outline
- Perfect gas
What is its property?
How to describe it? : Perfect gas equation

- Pure gas vs. mixture of gases

- Real gases
How are they different from the perfect gas?

How to describe the behavior of them?

Compression factor
Virial equation of state

Van der Waals equation

The principle of corresponding states

Properties of gas
- collection of molecules in continuous random motions

- average speed increases as the temperature increases.

- molecules in a gas are widely separated from one another.
- molecules in a gas move in paths that are mostly unaffected by

intermolecular forces( most of the time, molecules move without

any interactions)
- intermolecular interactions are negligible
repulsive interaction

attractive interaction

The states of gases

- physical properties: physical state or physical condition of a
substance
- state of pure gas can be specified by

number of moles, n
pressure, p
volume, V
temperature, T
- equation of state: interrelation of variables

p = f(T,V,n) : if we know T, V, n,
then pressure has a fixed value.
for perfect gas p = nRT/V

Pressure
- pressure = force divided by the area to which the force is applied
p = F/A
- [unit] pascal(Pa):

Pa = N/m2 = kg/ms2

1 bar: standard pressure for reporting

mecahnical equilibrium:
if two regions with high and low pressures is separated

by movable wall the wall will be pushed from the

high pressure region until when both pressures
become equal

The measurement of pressure

- barometer: invented by Torricelli
- column of liquid of density and height h

at the surface of the earth

F = mg = (V)g = (Ah)g ,
p = F/A = Ahg/A = hg

Temperature
- indicated the direction of the flow of energy
through thermally conducting wall
- boundary

diathermic: conducting
adiabatic: insulating

- Energy flows as heat through diathermic wall

from high T to low T until thermal equilibrium

Zeroth law of thermodynamics

: if A is thermal equilibrium with B, and B is in thermal equilibrium with C, then
C is also in thermal equilibrium with A
- measuring the temperature
- : Celsius scale, [oC]

- K : Kelvin scale : T = + 273.15 [K]

The perfect gas law

-Boyles law: pressure volume dependence of perfect gas
pV = constant, at constant n, T

Isotherm: variation of the pressure of a gas a the volume

change at constant temperature

Charless law
V = constant x T,

at constant n, p
V1/T1 = V2/T2

isobar: variation of volume of a gas

with temperature changes at
constant pressure

p= constant x T,

at constant n, V
P1/T1 = p2/T2

isochores: variation of pressure of a gas

with temperature changes at
constant volume

- Boyles law: pV = constant, at constant n, T

- Charless law: V = constant x T, at constant n, p
p= constant x T, at constant n, V

- Avogadros principle: V = constant x n, at constant p

Perfect gas equation

pV = nRT
R = gas constant

*Boyles and Charless laws are

limiting law (strictly try on in a
certain limit i.e. low pressures or
high temperatures)

Ex 1.2) 100 atm, 300 K 500 K, p = ?

R = pV/nT p1V1/T1 = p2V2/T2
p2 = T1/T1 x p1 = 500 K/300 K x100 atm = 167 atm

Mixtures of gases
- Partial pressure: pJ = xJp xJ: mole fraction of component J
xJ = nJ/n, n= nA + nB +
- Total pressure: p = pA + pB + = (xA + xB + )p

- Daltons law for a mixture of gases

: The pressure exerted by a mixture of gases is the sum of the

pressures that each one would exert if it occupied the container

alone
- Partial pressure of perfect gases

Composition of dry air at sea level

Ex) The mass percentage composition of dry air at sea level is approximately
N2:O2:Ar = 75.5:23.2:1.3. What is the partial pressure of each component

when the total pressure is 1.20 atm?

answer: number of mole of each gas for 100 g of air

n(N2) = (75.5 g)/(28.02 g/mol) = 2.69 mol

n(O2) = (23.2 g)/(32.00 g/mol) = 0.725 mol

n(Ar) = ( 1.3 g)/(39.95 g/mol) = 0.033 mol

total = 3.45 mol

mole fraction
x(N2) = 2.69 mol/3.45 mol = 0.780
x(O2) = 0.725 mol/3.45 mol = 0.210
x(Ar) = 0.033mol/3.45 mol = 0.0096
partial pressure: pJ = xjp
p(N2) = 0.780 x 1.2 atm = 0.936 atm
p(O2) = 0.210 x 1.2 atm = 0.252 atm
p(Ar) = 0.0096 x 1.2 atm = 0.012 atm

The kinetic model of gases

- Assumptions for kinetic model of gases
1. The gas consists of molecules of mass m in ceaseless random motion.
2. The size of molecules is negligible, in the sense that their diameters are

much smaller than the average distance travelled between collisions.

3. The molecules interact only through brief, infrequent, and elastic collisions.

- elastic collision: total translational kinetic energy is conserved.

- from kinetic model of gases

pV = 1/3nMvrms2, M = mNA, molar mass

-

pV = nRT

vrms = (2), = speed of the molecules

molecular speed vs temperature

- Pressure arises from the impact of molecules on the wall

pressure

The Maxwell-Boltzmann distribution of speeds

-

- mean values

1, 2 =

mean speed of perfect gas: mean = 8

1 2

most probable speed of perfect gas: mp = 2

=

: mean = 3 8
mp = 2 3

1 2

1 2

1 2

Collisions

collision frequency : = ,
collision cross-section: = 2
mean relative speed: mean speed of one molecule approaches another
: rel = 8
A B

1 2

, =

A + B , ;

mean free path: average distance a molecule travels between collisions

= rel =

Real gases
- do not obey the perfect gas law exactly except in the limit of p 0
- deviation from the law are particularly important at high pressure and low T.

Molecular interactions
- repulsive forces(short range)
- attractive forces: important when the molecules

are fairly close

- repulsive forces assist expansions

attractive forces assist compressions

Variation of the potential

energy of two molecules on
their separation

The compression factor

- Z: the ratio of its measured molar volume(Vm) to the molar volume of a
perfect gases(Vmo) at the same pressure and temp

, Vmo = RT/p for perfect gas

Z = pVm/RT pVm = RTZ
- deviation of Z from 1

departure from perfect behavior

- Z = 1 : perfect gas,
~ 1 : low pressure

> 1 : high pressure, Vm > Vm0

repulsive interaction
< 1 : intermediate pressure, Vm < Vm0
attractive interaction

Virial coefficients
- at large molar volume and high temperature
real gases do not obey the perfect gas law power of variables
- Virial equation of state(p or V)

pVm = RT(1 + Bp + Cp2 + )

pVm = RT(1 + B/Vm + C/Vm2 + )

B, C, : virial coefficient depend on T

B/Vm C/Vm2

- Virial equation can be written with Z

pVm = RTZ Z = 1 + Bp + Cp2 +

= 1 + B/Vm + C/Vm2 +
- for perfect gas: Z = 1, dZ/dp = 0
- for real gas: Z 1 as p 0
dZ/dp B as Vm
dZ/d(1/Vm) B as Vm

- Boyle temperature TB, B = 0

: At TB, : properties of the real gas do coincide with those of perfect gas
C/Vm2 and higher terms are negligibly small
- Temperature dependence of B
at high T, dZ/dp B(T) > 0 as p 0
at low T, dZ/dp B(T) < 0 as p 0

at TB

dZ/dp = 0 as p 0

Second order viral coefficients. B/(cm3/mol)

Condensation
- Condensation: At low temperature a gas changes to a liquid.

- Vapor pressure: pressure of the gas in equilibrium with the liquid at a certain T
- Isotherm at 20oC A B C D E F

A B: V decreases when p increases

at C: V decreases without p increases
liquid formation started

C D E: liquid increases
p = vapor pressure of liquid

E F: liquid compression
small volume decreases
with large p increases

Critical constant
- critical point: the point where a gas phase and a liquid phase are not

separated
- critical constant: pc, Vc, Tc
- below Tc: gas condensed to liquid when it pressurized
- above Tc: no phase separation between liquid and gas
- supercritical fluid: T > Tc single phase
Critical constants

The van der Waals equations

- for real gases,
repulsive and attractive interactions between molecules
molecules have volume reduce the total volume available

attractive interaction reduce the pressure

Formulation of the equation

- van der Waals equation:

Vm = V/n

- van der Waals coefficients

a: represents the strength of attractive interaction

b: repulsive interaction, related with the volume of molecules

- a, b correlated with critical temperature, vapor pressure, and enthalpy of

vaporization reflect the strength of intermolecular interaction

Repulsive interaction
- consider the volume of molecules

V - nb, nb: approximately the total volume o taken by the molecules

themselves

p = nRT/V p = nRT/(V-nb), when repulsion is significant

- Hard-sphere molecule with radius r
Vmolecule = 4/3r3 volume excluded = 4/3(2r)3

volume excluded per molelcule = 4Vmolecule

b ~ 4VmoleculeNA

- Intermolecular interaction b

van der Waals coefficients

Attractive interaction
- pressure depends on collision frequency and force of each collision
both are reduced by the attractive forces
strength the molar concentrations, n/V

reduce the pressure = -a(n/V)2

- intermolecular interaction a

- small a weak interaction

The features of the equation

- virial equation(experimental coefficients) should use for numerical analysis.
Equation of states

- van der Waals equation: it is not perfect but analytical

provide some general conclusions about he real gases

Features of van der Waals equation

- perfect gas isotherms are obtained at high T and large molar volumes

(Vmb)

- liquids and coexist when cohesive and dispersing effects are in balance
- the critical constants are related to the van der Waals coefficients.
at critical point(T = Tc)
2 + 2a/V 3
dp/dVm = 0 = - RT/(Vm-b)
m

d2p/d2Vm = 0 = 2RT/(Vm-b)3 6a/Vm4

Vc = 3b, pc = a/27b2, Tc = 8a/27Rb

critical compression factor

Zc = pcVc/RTc = 3/8

van der Waals isotherms

with different T/Tc

The principle of corresponding states

- Reduced variables(dimensionless)
Vr = Vm/Vc, pr = p/pc, Tr = T/Tc p = prpc, T = TrTc, Vm = VrVc
- van der Waal equation by reduced variables

p = RT/(Vm-b) a/Vm2 prpc = RTrTc/(VrVc-b) a/Vr2Vc2

Vc = 3b, pc = a/27b2, Tc = 8a/27Rb

isotherms based on reduced variables

are the same curves for all gases

T/Tc

Exercises: 1A.7(b), 1B.3(b), 1C.6(a)

Problems: 1A.2, 1B.3,1C.9