Chapter 3 Real gases

Chemical Thermodynamics : Georg Duesberg

Chapter11111 Chapter 1 : 1Slide : Slide 1 1

 Perfect gas: only contribution to energy is KE of molecules Real gases: Molecules interact if they are close enough, have a potential energy contribution. At large separations, attractions predominate (condensation!) At contact molecules repel each other (condensed states have volume!)
Ideal (Isotherms) Real (CO2)
F

Real Gases

Thermo meter Pressure gauge

Chemical Thermodynamics : Georg Duesberg

Deviations from ideality can be described by the COMPRESSION FACTOR, Z (sometimes called the compressibility). Z = pV/(nRT) = pVm/(RT) For ideal gases Z = 1
Pressure region I (very Low) II (moderate) III (high) Molecules have large separations -> no interactions -> Ideal Gas Behavior: Z =1 Molecules are close -> attractive forces apply -> The gas occupies less volumes as expected from Boyles law: Z<1 Molecules compressed highly -> repulsive forces dominate -> hardly further decrease in volume Z>1

Chemical Thermodynamics : Georg Duesberg

Chapter33333 1 : Slide 3

Microscopic interpretation: Leonard Jones Potential

When p is very high, r is small so shortrange repulsions are important. The gas is more difficult to compress than an ideal gas, so Z > 1. When p is very low, r is large and intermolecular forces are negligible, so the gas acts close to ideally and Z 1. At intermediate pressures attractive forces are important and often Z < 1.
Chapter 1 : Slide 4 Chemical Thermodynamics : Georg Duesberg

Real Gases: What happens if we press down the piston

( at 20 C, gas: carbon dioxide) A B perfect gas behavior (isotherm) B C slight deviation from perfect behavior less pressure than expected C D E no change in pressure reading over further compression but increasing amount of liquid observed E F : steep in crease in P, only liquid visible (At contact molecules repel each other condensed states have volume!)

The line C D E is the vapour pressure of a liquid at this tempeature

5 Chemical Thermodynamics : Georg Duesberg

Deviations from ideality can be described by the COMPRESSION FACTOR, Z (sometimes called the compressibility). Z = pV/(nRT) = pVm/(RT) For ideal gases Z = 1 Attractive forces vary with nature of gas At High Pressures repelling forces dominate

Z=

Chemical Thermodynamics : Georg Duesberg

Deviations from ideality can be described by the COMPRESSION FACTOR, Z (sometimes called the compressibility). Z = pV/(nRT) = pVm/(RT) For ideal gases Z = 1 At Low Temperatures the attractive regime is pronounced higher Temperature ->faster motion -> less interaction

Z=

7 Chemical Thermodynamics : Georg Duesberg

Boyle Temperatur
The temperature at which this occurs is the Boyle temperature, TB, and then the gas behaves ideally over a wider range of p than at other temperatures. Each gas has a characteristic TB, e.g. 23 K for He, 347 K for air, 715 K for CO2.

The compression factor approaches 1 at low pressures, but does so with different slopes. For a perfect gas, the slope is zero, but real gases may have either positive or negative slopes, and the slope may vary with temperature. At the Boyle temperature, the slope is zero and the gas behaves perfectly over a wider range of conditions than at other temperatures. Chapter 1 : Slide 8
Chemical Thermodynamics : Georg Duesberg

Most fundamental and theoretically sound Polynomial expansion Viris (lat.): force (Kammerling Onnes 1901) Virial coefficients: p Vm = RT (1 + Bp + Cp2 + ...) i.e. p Vm = RT (1 + B/Vm + C/Vm2 + ...) This is the virial equation of state and B and C are the second and third virial coefficients. The first is 1. B and C are themselves functions of temperature, B(T) and C(T). Usually B/Vm >> C/Vm2 B = 0 at Boyle temperature Also allow derivation of exact correspondence between virial coefficients and intermolecular interactions

Virial Equation of State

Real gas Van der Waals equation.

ideal gas : PV = nRT

(P + x )(V y ) = nRT
a n RT P + a ( V nb ) = nRT or P = V V b V m m
2 2

Johannes Diderik van der Waals got the Noble price in physics in 1910
Chapter1010101010 1 : Slide 10

Chemical Thermodynamics : Georg Duesberg

Real gas Van der Waals equation: b

1. The molecules occupy a significant fraction of the volume. -> Collisions are more frequent. -> There is less volume available for molecular motion. Real gas molecules are not point masses (Vid = Vobs - const.) or Vid = Vobs - nb b is a constant for different gases Very roughly, b 4/3 r3 where r is the molecular radius. Other explanation: What happens if we reduce T to zero. Is volume of the gas, V, going to become zero? We can set P 0. By the ideal gas law we would have V = 0, which cannot be true. We can correct for it by a term equal to the total volume of the gas molecules, when totally compressed (condensed) nb. Now at T = 0 and P 0 we have V = nb.

P(V nb) = nRT

Chemical Thermodynamics : Georg Duesberg

Chapter 1 : Slide 11

Real gas Van der Waals equation: a

2) There are attractive forces between real molecules, which reduce the pressure: p wall collision frequency and p change in momentum at each collision. Both factors are proportional to concentration, n/V, and p is reduced by an amount a(n/V)2, where a depends on the type of gas. [Note: a/V2 is called the internal pressure of the gas]. Real gas molecules do attract one another (Pid = Pobs + constant) Pid = Pobs + a (n / V)2 a is also different for different gases

n a 2 V
Chemical Thermodynamics : Georg Duesberg

a describes attractive force between pairs of molecules. Goes as square of the concentration (n/V)2 .

Van der Waals equation of state

2 n P + a (V nb ) = nRT or P = RT a V V V b m m
a/(atm dm mol ) 1.4 4.169 1.338 3.610 5.507 4.552 0.0341 0.2420 1.352 1.364 4.137
6 2

Substance Air

b/(10 dm mol ) 0.039 3.71 3.20 4.29 6.51 5.82 2.38 2.65 3.87 3.19 5.16

Ammonia, NH3 Argon, Ar Carbon dioxide, CO2 Ethane, C2H6 Ethene, C2H4 Helium, He Hydrogen, H2 Nitrogen, N2 Oxygen, O2 Xenon, Xe

If 1 mole of nitrogen is confined to 2l and is at P=10atm what is Tideal and TVdW?

Tip: R =0.082dm3atmK-1mol-1

Parameters depend on the gas, but are taken to be independent of T. a is large when attractions are large, b scales in proportion to molecular size 13 (note units)
Chemical Thermodynamics : Georg Duesberg

CONDENSATION or LIQUEFACTION This demonstrates that there are attractive forces between gas molecules, if they are pushed close enough together. E.G. CO2 liquefies under pressure at room temperature. Above 31 0C no amount of pressure will liquefy CO2: this is the CRITICAL TEMPERATURE, Tc.
Chapter 1 : Slide 14 Chemical Thermodynamics : Georg Duesberg

Carbon dioxide: a typical pV diagram for a real gas:

Experimental isotherms of carbon dioxide at several temperatures. The `critical isotherm', the isotherm at the critical temperature, is at 31.04 C. The critical point is marked with a star.

Tc, pc and Vm,c are the critical constants for the gas. The isotherm at Tc has a horizontal inflection at the critical point dp/dV = 0 and d2p/dV2 = 0. Chapter 1 :

Chemical Thermodynamics : Georg Duesberg

At the critical temperature the densities of the liquid and gas become equal - the boundary disappears. The material will fill the container so it is like a gas, but may be much denser than a typical gas, and is called a 'supercritical fluid'. The isotherm at Tc has a horizontal inflection at the critical point dp/dV = 0 and d2p/dV2 = 0. Consider 1 mol of gas, with molar volume V, at the critical point (Tc, pc, Vc) 0 = dp/dV 0 = d2p/dV2 = -RTc(Vc-b)-2 + 2aVc-3 = 2RTc(Vc-b)-3 - 6aVc-4

Critical Point

The solution is Vc = 3b, pc = a/(27b2), Tc = 8a/(27Rb).

Chemical Thermodynamics : Georg Duesberg

16

Critical Point drying

Applications: TEM sample prep, porous materials, MEMS

Chemical Thermodynamics : Georg Duesberg

Chapter1717171717 1 : Slide 17

CNT

Chemical Thermodynamics : Georg Duesberg

Metal contacts on CNT

Chemical Thermodynamics : Georg Duesberg

Etch

Chemical Thermodynamics : Georg Duesberg

Freely suspended CNT

Etch

Chemical Thermodynamics : Georg Duesberg

TEM electron beam

Freely suspended CNT

Etch

Chemical Thermodynamics : Georg Duesberg

Protective resist Etch

Chemical Thermodynamics : Georg Duesberg

Protective resist

Etch

Chemical Thermodynamics : Georg Duesberg

Chemical Thermodynamics : Georg Duesberg

Chemical Thermodynamics : Georg Duesberg

Chemical Thermodynamics : Georg Duesberg

Chemical Thermodynamics : Georg Duesberg

Suspended on contacted individual CNTs Platform for combined investigations

Structure and Electronic Properties can be related: Individual tubes or bundels? What kinds of CNT (MWCNT, SWCNT, (n,m), peapods..)

Chemical Thermodynamics : Georg Duesberg

Combined TEM and Raman investigations on individual

SWCNTs

Chemical Thermodynamics : Georg Duesberg

Maxwell Construction
Below Tc calculated vdW isotherms have oscillations that are unphysical. In the Maxwell construction these are replaced with horizontal lines, with equal areas above and below, to generate the isotherms. (The line is the vapour pressure of a liquid at this temperature, or liquid-vapor equilibrium)

31 Chemical Thermodynamics : Georg Duesberg

Features of vdW equation

Reduces to perfect gas equation at high T and V Liquids and gases coexist when attractions repulsions Critical constants are related to coefficients. Flat inflexion of curve when T=Tc. Can derive (by setting 1st and 2nd derivatives of equation to zero) expression for critical constants Vc = 3b, pc = a/27b2, Tc =8a/27Rb Can derive expression for the Boyle Temperature TB = a/Rb
32 Chemical Thermodynamics : Georg Duesberg

Features of vdW equation

Can derive (by setting 1st and 2nd derivatives of equation to zero) expression for critical constants

2 p p we have, i.e., = 0 and = 0 v 2 v T =Tc T =Tc

RT 2a p = + 3 2 v v T (v b)

P=

RT a 2 vb v

2 p 2 RT 6a and v 2 = (v b )3 v 4 T
2 RT 6a 4 =0 v

At critical points the above equation reduces to

RT

(v b )
33 Chemical Thermodynamics : Georg Duesberg

2a + 3 =0 v

and

(v b )3

By dividing those equations and simplifying we get

Features of vdW equation

We also can say

vc b= 3

RTc a Pc = 2 vb v

Substituting for b and solving for a from 2nd derivative we get, a = 9RTcvc Substituting these expressions for a and b in equation (P(c) and solving for vc, we get
3RTc vc = 8 pc

RTc b = 8 pc

27 R T and a = 64 pc

2 c

Note: Usually constants a and b for different gases are given.

Chemical Thermodynamics : Georg Duesberg Chapter3434343434 1 : Slide 34

Critical constants
pc atm Ar CO2 He O2 48.0 72.9 2.26 50.14 Vc
cm3/mol

Tc K 150.7 304.2 5.2 154.8

Zc 0.292 0.274 0.305 0.308

TB K 411.5 714.8 22.64 405.9

75.3 94.0 57.8 78.0

The general Van der Waals pVT surface

Chemical Thermodynamics : Georg Duesberg

The principle of corresponding states

Gases behave differently at a given pressure and temperature, but they behave very much the same at temperatures and pressures normalized with respect to their critical temperatures and pressures. The ratios of pressure, temperature and specific volume of a real gas to the corresponding critical values are called the reduced properties. Define reduced variables pr = p/pc Tr = T/Tc Vr = Vm/Vm,c

Van der Waals hoped that different gases confined to the same Vr at the same Tr would have the same pr.

Chapter 1 : Slide 36 Chemical Thermodynamics : Georg Duesberg

Proof: rewrite Van der Waals equation for 1 mol of gas, p = RT/(V-b)a/V2, in terms of reduced variables:

RTr Tc a pr pc = 2 2 Vr Vc b Vr Vc
pra RTr 8a a = 2 2 2 27b 27Rb(Vr 3b b) Vr 9b

Substitute for the critical values:

Thus

8Tr 3 pr = 2 3Vr 1 Vr
Also:

Thus all gases have the same reduced equation of state (within theVan derWaals approximation).

Zc =pcVc/RTc = 3/8 =0.375

Chemical Thermodynamics : Georg Duesberg

With reduced variables, different gases fall on the same curves -> Degree of generality ( principle of corresponding states) According to this law, there is a functional relationship for all substances, which may be expressed mathematically as vR = f (PR,TR). From this law it is clear that if any two gases have equal values of reduced pressure and reduced temperature, they will have the same value of reduced volume. This law is most accurate in the vicinity of the critical point.

Principle of Corresponding States

Compression factor plotted using reduced variables. Different curves are different TR

The compressibility factor of any gas is a function of only two properties, usually temperature and pressure so that Z1 = f (TR, PR) except near the critical point. This is the basis for the generalized compressibility chart. The generalized compressibility chart is plotted with Z versus PR for various values of TR. This is constructed by plotting the known data of one or more gases and can be used for any gas.

It may be seen from the chart that the value of the compressibility factor at the critical state is about 0.25. Note that the value of Z obtained from Van der waals equation of state at the critical point,

The following observations can be made from the generalized compressibility chart:

Pc vc 3 which is higher than the actual value. Zc = = RTc 8

At very low pressures (PR <<1), the gases behave as an ideal gas regardless of temperature. At high temperature (TR > 2), ideal gas behaviour can be assumed with good accuracy regardless of pressure except when (PR >> 1). The deviation of a gas from ideal gas behaviour is greatest in the vicinity of the critical point.

There are many other equations of state for real gases

1) The Berthelot Equation. Replace Van der Waals' "a" with a temperature dependent term, a/T: [p + a/(Vm2T)] [Vm - b] = RT 2) The Dieterici Equation : [p exp(a/VmRT)] [Vm - b] = RT 3) Redlich-Kwong 4) Peng-Robinson
p=

p=

RT A 1/ 2 Vm B T Vm (Vm + B)

RT Vm Vm (Vm + ) + (Vm )

Redlich-Kwong, Peng-Robinson are quantitative in region where gas liquefies Berthelot,Dieterici and others with more than ten parameters can give good fits with four free parameters, you can describe an elephant. With five his tail is Chapter 1 : Slide 41 rotating
Chemical Thermodynamics : Georg Duesberg

Summary: Real gases

REAL GASES: the COMPRESSION FACTOR and INTERMOLECULAR FORCES. pV diagrams: LIQUEFACTION and the CRITICAL POINT. BOYLE TEMPERATURE The VAN DER WAALS approximate equation of state p = RT/(Vm-b) a/Vm2 is more realistic for REAL GASES. There are other equations of state which work well e.g The VIRIAL EQUATION REDUCED VARIABLES and the PRINCIPLE OF CORRESPONDING STATES Pressure region
I (very Low) II (moderate) III (high)
Chemical Thermodynamics : Georg Duesberg

Molecules have large separations -> no interactions -> Ideal Gas Behavior: Z =1 Molecules are close -> attractive forces apply -> The gas occupies less volumes as expected from Boyles law: Z<1 Molecules compressed highly -> repulsive forces dominate -> hardly further decrease in volume Z>1
Chapter 1 : Slide 42

Real gas Van der Waals equation.

For nitrogen a=0.14 and b=3.87x10-5. If 1.0 mole of nitrogen is confined to 2.00l and is at P=10atm what is Tideal and TVdW?
PV = nRT PV / nR = T 10 2/1 0.082 = 244
2 n P + a (V nb ) = nRT V 2 n P + a (V nb ) / nR = T V 2 1 1 + 0.14 (2 1 0.0387 ) / 1 0.082 = 240 2

Under these conditions the temperature only changes by ~1%.

Chapter 1 : Slide 43 Chemical Thermodynamics : Georg Duesberg