State variables

Thanks to molecular chaos, ergodic motion, and the existence of equilibrium states, the macroscopic state of the system is described by a handful of macroscopic state variables (and not ~1023 positions and momenta!). For a one component system, 3 state variables are usually needed to completely specify the state of the system, one of which must be an extensive variable. They may be T, V, n T, P, n T, V, ( = n/V) T, P, (why not?) Extensive: V, n, Intensive: P, , V,( V = V / n )

Equations of state
A relationship giving a macroscopic variable in terms of others is called an equation of state. P = P(V,T,n) is a common equation of state. The ideal gas law is of this form. P = nRT/V . An intensive variable like P can be written as a function of only two other intensive variables. For example, P = P(T,) where = n/V . The ideal gas law can be written as P = RT . It is the special properties of systems in equilibrium (molecular chaos, ergodic motion) that permit state variables to be functions of a handful of other state functions, and equations of state to exist.

Other equations of state

U = U ( P, T , n) V = V (U , P, n) S = S (V , T , n) S = S (T , ) S n S = , = n V

Partial derivatives
For an example, take f to be a function of three variables, x,y,z.

f = f ( x, y , z ) f ( x + dx, y, z ) f ( x, y, z ) f = lim dx 0 dx x y , z f f ( x, y + dy, z ) f ( x, y, z ) = lim y dy 0 dy x, z f ( x, y, z + dz ) f ( x, y, z ) f = lim dz 0 dz z x , y

A partial derivatives is an ordinary derivative with respect to one of the variables, holding the other variables constant.

For a system that is a mixture of c components, an extensive property is a function of c+2 state variables, one of which is extensive. An intensive property is a function of c+1 intensive state variables.

S = S (V , T , n1 , n2 , n3 ) (3 components, c + 2 = 5)

2 components, c + 1 = 3, S = S (V , T , x1 ) n1 S S = , x1 = , n = n1 + n2 n n

2000

Isotherms and isobars

1750 1500 1250

slope of isotherms isotherms

V(L)

1000 750 500 250 0 2 4 6 8 10

V P T ,n

Understanding partial derivatives on a mathematical level

P(Pa)

The equation of state is a 2-dimensional surface in a 3-dimensional space with axes labeled by P,T,V.
V(L)
1500

V(L)
2000 1000 0 0 2.5 5 7.5 400

The variables on the bottom are the independent variables.

V P T ,n

Regard V as a function of the independent variables P,T,n.

T(K)
200

slope of isobars

1250 1000 750 500 250 0

isobars

V T P ,n

P(Pa)

10

V P T ,n tells you the slope of the isotherms.

100

200

300

400

500

T(K)

Understanding partial derivatives on a physical level

1 V V , or T = , which is normalized by V to V P T ,n P T ,n
make T a positive intensive quantity, is a linear response function or susceptibility. perturbation response A susceptibility gives the response to an external perturbation. In this case T tells you how volume responds to a pressure change.

The susceptibility gives the linear response

T =
T tells you how volume responds to a pressure change.

1 V , is a linear response function or susceptibility. V P T ,n

V V , for small V and P, constant T = P T ,n P V V = P , linear response of volume to P P T ,n

V

1 V V = P = T P V V P T ,n

Gases at 1 atm are nearly ideal

At 1atm ( 1 bar) gas molecules are about 3.5nm (35) apart. Intermolecular interactions can be neglected.

Gases at 1 atm are nearly ideal

At 1atm ( 1 bar) gas density is ~ 2.4 x 102 molecules/nm3. Density of liquid water is 33.4 molecules/nm3.

~3

Real gases
Gases deviate from ideal behavior at high pressure or density, or at low temperature. Deviations from PV=nRT are caused by interactions between molecules.

Real gases
Gases deviate from ideal behavior at high pressure or density, or at low temperature. Deviations from PV=nRT are caused by interactions between molecules.

1 mol of N2, CH4, H2 at 300K, CO2 at 313K 1 mol of N2

Intermolecular interactions
The interaction between molecules is typically repulsive at very short distances, attractive at longer distance.

Excluded volume
The volume available to molecules in a gas is reduced by the volume of other molecules. This effect is known as excluded volume.

The actual volume available to a molecule is V nb, where b is the volume excluded by 1 mole of gas and n is the number of moles.

Replace V by V nb in the ideal gas law. The effect of excluded volume is to raise the pressure.

P=

nRT V nb

b describes molecule volume

m3/mol x105

Molecular attractions
Attractive interactions will cause the gas molecules to pull together, strike the walls with less force, and decrease the pressure.

The b values you find in tables are fit to experimental equations of state.

The ideal gas law is corrected by an extra term that lessens the pressure.

P=

n n nRT n a RT a = V V V V

Molecular attractions

The van der Waals equation

The effects of attractions and repulsions are 2 nRT n combined in an empirical gas law, the van P= a der Waals equation. a and b are chosen to V nb V match experimental data.

n n nRT n P = RT a = a V V V V

The correction term is proportional to density (n/V) because the effect is only important when the gas is sufficient dense for molecules to feel each other. At low density, the correction should vanish. The constant a reflects the strength of attractions between molecules.

The van der Waals equation is sometimes written these equivalent forms.

2 P + a n (V nb ) = nRT V

a P + 2 V b = RT V

Common two-parameter equations of state

van der Waals

A generic phase diagram in the P-V plane

fluid critical point

P=

RT a 2 V b V

Redlich-Kwong

RT A P= 1 V B T 2V V + B

)
)

vapor P liquid

Peng-Robinson

P=

RT V V V + + V

) (

solid triple point

Redlich-Kwong and Peng-Robinson better reproduce experimental data (see text book).

Coexistence regions
fluid critical point vapor P liquid liquid-vapor coexistence solid triple point solid-vapor coexistence V Tie lines are shown

Spontaneous phase separation in coexistence regions

equilibrate

If prepared in a homogeneous state within a coexistence region, a substance will spontaneously separate into two coexisting phases.

Continuous path from liquid to vapor above the critical point

fluid critical point vapor P liquid

Isotherms within the P-V plane

fluid critical point P liquid

solid triple point V

solid triple point V

Super-critical, critical, and subcritical isotherms, as you would calculate from vdW, RedlichKwong, or PengRobinson equations of state vapor are shown

Super-critical isotherm within the P-V plane

fluid critical point

Critical isotherm within the P-V plane

fluid critical point

P < 0, T > 0 V T everywhere along the super-critical isotherm.

P liquid

P < 0, T > 0 V T everywhere along critical isotherm,

except at critical point where P = 0, T = V T

liquid

solid triple point V

1 V vapor T = V P T , n = 1 V P V T ,n
1

solid triple point V

2P and 2 = 0 V T vapor because slope is maximum at critical point.

Sub-critical isotherm within the P-V plane

fluid critical point a liquid b solid triple point V c d e Between points b and d,

Sub-critical isotherm within the P-V plane

equilibrate fluid

P > 0, T < 0 V T
V = T P, Since V the substance expands as pressure vapor increases between points b and d!?
P a liquid b solid triple point V c d e

The substance is within the coexistence region between a and e.

Curves predicted by vdW,R-K,P-R, are for hypothetical onephase system, which vapor is less likely than coexisting liquid and vapor between a and e.

Sub-critical isotherm within the P-V plane: Maxwell equal-area construction

fluid critical point a liquid b solid triple point V c d e The region where two phases are more stable (more likely) than one phase is predicted by

Procedure to find critical parameters

P function of T,V,n.
fluid

P = P (V , T , n) = P(V , T )

critical point

liquid

Areaabc = Areacde
This is called the Maxwell equal-area vapor construction, which we will justify later.

P =0 V T , n
vapor

2 eq.s in 2 unknowns, T,V. Solve to find Tc, Vc.

solid triple point

2P V 2 = 0 T , n

Plug Tc, Vc.into P(T,V) to obtain Pc.

work out van der Waals critical point as example

Critical parameters of van der Waals gas

vdW equation

Critical parameters of van der Waals gas

vdW equation

P=

RT a 2 V b V

See text book for an alternative derivation of critical parameters

1 q 2a P = RT 2 , where q = RT V b 2V
Set

P=
Think of q as an alternative temperature variable

RT a 2 V b V

1 2a q 2 , where q = P = RT RT V b 2V
1st derivative = 0

P =0 V T ,n

and

2P 2 =0 V T ,n

1 q P + 3=0 = RT 2 V T ,n V b V

The value of q at the critical point is qc =

2a . RTc

V = q V b

Critical parameters of van der Waals gas

vdW equation P = RT
3

Critical parameters of van der Waals gas

vdW equation P = RT

1 q 2a 2 , where q = RT V b 2V

1 q 2a 2 , where q = RT V b 2V

1st derivative = 0 V = q V b 2nd derivative = 0

2nd derivative = 0 V = 1st

3

3 3q V b 2

P 2 V T ,n
2

2 3q = RT 4=0 3 V b V

derivative = 0 V = q V b

divide these two equations

Vc =

3 V c b 2

at critical point

3 3q V = V b 2 4

V c = 3b

Critical parameters of van der Waals gas

vdW equation P = RT

Critical parameters of van der Waals gas

vdW equation P = RT critical volume critical temperature

1 q 2a 2 , where q = RT V b 2V

1 q 2a 2 , where q = RT V b 2V

3 3q 2nd derivative = 0 V = V b 2 4

V c = 3b qc = 8a 27b , Tc = 27 Rb 4

1st derivative = 0 V = q V b critical volume

V c = 3b

plug back in to get qc and Tc

q 1 Pc = RTc c2 V c b 2V c

(3b )3 = qc (3b b )2
qc = 27b 4

Since qc =

2a , RTc

2a 27b = RTc 4 Tc = 8a 27 Rb

27 27b a 8 1 8a 1 4 = a 8 1 3 4 = Pc = R 2 2 2 2 27 Rb 3b b 2(3b ) b 27 3 1 2(3) b 27 2 8

( )

Pc =

a 27b 2

Critical parameters of van der Waals gas

vdW equation P = RT critical volume critical temperature

Reduced variables and corresponding states

We will reach the surprising conclusion that in the right units all substances obey nearly the same equation of state. Construct dimensionless variables:

1 q 2a 2 , where q = RT V b 2V

V c = 3b

27b 8a qc = , Tc = 4 27 Rb

PR =

a critical pressure Pc = 27b 2

critical PVc compressibility Z c = c RTc factor

Zc is independent of the substance! This gives us a hint that constructing a dimensionless (3b ) 3 27b 2 quantities will = = 8a 8 produce R 27 Rb simplifications.

P T V , TR = , V R = Pc Tc Vc

Substitute P = PR Pc , T = TRTc , V = V R V c into the

van der Waals equation of state,

a P + 2 V b = RT V

The van der Waals equation in universal form

Substitute P = PR Pc , T = TRTc , V = V R V c into the
van der Waals equation of state, P + a V b = RT 2 V a P P + V R V c b = RT T R c R c 2 V RV c

Two-parameter equations of state

Any two-parameter equation of state can, in principle, be transformed into universal form in reduced units. The reduction may be algebraically messy, but choosing introducing dimensionless units in principle gives us enough freedom to cancel two parameters that depend on the chemical nature of the substance. As long as a group of substances can be described by some twoparameter equation of state*, their equation of state in reduced variables will be universal. *even if this equation of state may not have been discovered yet!

a P a + V R 3b b = RT 8a R R 2 2 27b 27 Rb V R 3b

In reduced variables, all 3 1 8 PR + 2 V R = TR vdW gases obey a universal 3 3 V R equation of state.

10

Corresponding states
Z

Virial expansion: Z as a function of density or pressure

Z Except near the critical point TR = PR = 1 Z is smooth function of T, P or .

The fact that data from so many substances collapses onto a universal curve supports the corresponding states analysis. PR

PR

The virial expansion

Analyze the deviation from ideality in terms of a series expansion in either the density of the pressure. Density virial expansion:

The virial expansion

Analyze the deviation from ideality in terms of a series expansion in either the density of the pressure.

1 n = = (density) V V

Z=

PV B (T ) B3V (T ) B4V (T ) = 1 + 2V + + +L 2 3 RT V V V
PV = 1 + B2 P (T ) P + B3 P (T ) P 2 + B4 P (T ) P 3 + L RT

Z=

PV B (T ) B3V (T ) B4V (T ) = 1 + 2V + + +L 2 3 RT V V V

Z=

Pressure virial expansion:

PV Z= = 1 + B2 P (T ) P + B3 P (T ) P 2 + B4 P (T ) P 3 + L RT

The virial coefficients, BnV or BnP , are functions of T only.

11

Plot Z as a function of density

Z=

B (T ) B3V (T ) B4V (T ) PV = 1 + 2V + + +L 2 3 RT V V V PV = 1 + B2V (T ) + B3V (T ) 2 + B4V (T ) 3 + L Z= RT

T2

Virial expansion

Z=
Z=

B (T ) B3V (T ) B4V (T ) PV = 1 + 2V + + +L 2 3 RT V V V
PV = 1 + B2 P (T ) P + B3 P (T ) P 2 + B4 P (T ) P 3 + L RT

PV Z= RT

B2V (T2 ) > 0

TBoyle T1

The virial expansion converges quickly for gases.

=
B2V (T1 ) < 0

1 V

The virial coefficients can be calculated if the intermolecular potential is known, or Virial coefficient data can be used to infer the intermolecular potential.

B2V (TBoyle ) = 0

T1 < TBoyle < T2

Virial coefficients and the interatomic potential

The virial coefficient are functions of T (not P, V, or n) determined by the interatomic or intermolecular potential.

The virial expansion is a power series expansion

Z= Z= B (T ) B3V (T ) B4V (T ) PV = 1 + 2V + + +L 2 3 RT V V V PV = 1 + B2V (T ) + B3V (T ) 2 + B4V (T ) 3 + L RT V n V= , = n V

u(r)

u (r ) B 2V (T ) = 2 N A dr r exp k T 1 B 0
2

Virial coefficients for molecules involve angle integrals too. When u(r) = 0, the gas is ideal and all virial coefficients vanish. Typically only B2V(T) used to relate the interatomic potential to gas data.

If we know Z(T,) from the equation of state, how do we determine the virial coefficients? The technique is called Taylor series expansion.

12

Taylor series expansion generates a local polynomial approximation to a complicated function

The Taylor series expansion is a polynomial is (x x0).

1 d 2 f df 2 f ( x) = f ( x0 ) + (x x0 ) + 2 (x x0 ) 2! dx x = x dx x = x0 0 + 1 d3 f 1 d n f n 3 3 (x x0 ) + L + n (x x0 ) + L n! dx x = x 3! dx x = x 0 0

1 d 2 f 2 df f ( x) = f ( x0 ) + ( x x0 ) + 2 (x x0 ) + 2! dx x = x dx x = x0 0 n 1 d3 f (x x0 )3 + L + 1 d nf (x x0 )n + L n! dx x = x 3! dx 3 x = x 0 0
The derivatives of f(x) at x0 are needed to construct the Taylor series expansion. If (x x0) is small, (x x0)2 will be smaller, (x x0)3 smaller still, and we can hope that truncating the expansion will not cause much error.

Taylor expand sin(2x) about x0

sin( 2 x) = sin( 2 x0 ) + [2 cos(2 x0 )]( x x0 ) + + 1 [ 4 sin(2 x0 )](x x0 )2 2! 1 [ 8 cos(2 x0 )](x x0 )3 + 1 [16 sin(2 x0 )](x x0 )4 3! 4! 1 1 5 6 + [32 cos(2 x0 )]( x x0 ) + [ 64 sin( 2 x0 )]( x x0 ) + L 5! 6!

Expansion of sin(2x) about x0 = 1 through order 1

Taylor approximation

Expansion of sin(2x) about x0 = 1 through order 2

Taylor approximation x sin(2x) sin(2x) x

sin( 2 x ) sin( 2 x0 ) + [2 cos(2 x0 )]( x x0 )

sin(2 x) sin(2 x0 ) + [2 cos(2 x0 )](x x0 ) +

1 [ 4 sin(2 x0 )](x x0 )2 2!

13

Expansion of sin(2x) about x0 = 1 through order 3

Taylor approximation

Expansion of sin(2x) about x0 = 1 through order 4

Taylor approximation

sin(2x)

sin(2x)

sin(2 x) sin(2 x0 ) + [2 cos(2 x0 )](x x0 ) + + 1 [ 8 cos(2 x0 )](x x0 )3 3!

1 [ 4 sin(2 x0 )](x x0 )2 2!

sin(2 x) sin(2 x0 ) + [2 cos(2 x0 )](x x0 ) + +

1 [ 4 sin(2 x0 )](x x0 )2 2!

1 [ 8 cos(2 x0 )](x x0 )3 + 1 [16 sin(2 x0 )](x x0 )4 3! 4!

Expansion of sin(2x) about x0 = 1 through order 5

Taylor approximation

Expansion of sin(2x) about x0 = 1 through order 6

Taylor approximation

x sin(2x)

sin(2x)

sin(2 x) sin(2 x0 ) + [2 cos(2 x0 )](x x0 ) + +

1 [ 4 sin(2 x0 )](x x0 )2 2!

sin(2 x) sin(2 x0 ) + [2 cos(2 x0 )](x x0 ) + +

1 [ 4 sin(2 x0 )](x x0 )2 2!

1 [ 8 cos(2 x0 )](x x0 )3 + 1 [16 sin(2 x0 )](x x0 )4 3! 4! 1 5 + [32 cos(2 x0 )]( x x0 ) 5!

1 [ 8 cos(2 x0 )](x x0 )3 + 1 [16 sin(2 x0 )](x x0 )4 3! 4! 1 1 5 6 + [32 cos(2 x0 )]( x x0 ) + [ 64 sin( 2 x0 )]( x x0 ) 5! 6!

14

Expansion of sin(2x) about x0 = 1 through order 7

Taylor approximation

Expansion of sin(2x) about x0 = 1 through order 8

Taylor approximation

x sin(2x)

x sin(2x)

sin( 2 x) sin( 2 x0 ) + [2 cos(2 x0 )]( x x0 ) +

1 [ 4 sin(2 x0 )](x x0 )2 2! 1 1 1 3 4 5 + [ 8 cos(2 x0 )]( x x0 ) + [16 sin( 2 x0 )]( x x0 ) + [32 cos(2 x0 )]( x x0 ) 3! 4! 5! 1 1 6 7 + [ 64 sin( 2 x0 )]( x x0 ) + [ 128 cos(2 x0 )]( x x0 ) 6! 7!

sin( 2 x) sin(2 x0 ) + [2 cos(2 x0 )]( x x0 ) +

1 [ 4 sin(2 x0 )](x x0 )2 2! 1 1 1 3 4 5 + [ 8 cos(2 x0 )]( x x0 ) + [16 sin(2 x0 )]( x x0 ) + [32 cos(2 x0 )](x x0 ) 3! 4! 5! 1 1 1 6 7 8 + [ 64 sin(2 x0 )]( x x0 ) + [ 128 cos(2 x0 )](x x0 ) + [256 sin( 2 x0 )](x x0 ) 6! 7! 8!

Virial coefficients by Taylor expansion of Z =

PV RT

Virial coefficients by Taylor expansion of Z =

PV Z (0) = RT = 1 =0
dZ B2V (T ) = d = 0

PV RT

Expand Z(,T) about = n/V = 0. (The T dependence of Z is not shown explicitly on the next line.)

dZ 1 d 2Z 1 d 3Z Z ( ) = Z ( 0) + + 2 2 + 3 3 + L 2! d =0 3! d =0 d =0

B3V (T ) =
Compare with

1 d Z 2! d 2 =0
2

It would be more accurate to write these as partial derivatives with respect to .

Z = 1 + B2V (T ) + B3V (T ) 2 + B4V (T ) 3 + L

B4V (T ) = L

1 d 3Z 3! d 3 =0

15

Virial coefficients of the van der Waals gas

van der Waals equation of state

Second virial coefficient of the van der Waals gas

virial coefficients

nRT n P= a V nb V

a 2 n 1 B2V (T ) = b , B3V (T ) = b , L BnV (T ) = b RT

compressibility factor

PV V a = RT V b RT V
Taylor expansion

Z (T , ) =

a 1 1 b RT

1 V

B2V(T) vanishes at the Boyle temperature TBoyle.

TBoyle =

a bR

a 2 2 3 3 4 4 Z (T , ) = 1 + b + b + b + b + L RT

For T < TBoyle attractions dominate. For T > TBoyle repulsions dominate. When T = TBoyle attractions and repulsions cancel in B2V(T).

virial coefficients

a 2 n 1 B2V (T ) = b , B3V (T ) = b , L BnV (T ) = b RT

The Boyle temperature and ideality

It is often said that a gas behaves as if ideal at the Boyle temperature. This is only in regards to B2V(T). Even at TBoyle the other virial coefficients are not zero. There are other possible measures of the cancellation between attractions and repulsions, for example Z =1.

Z=1
1 mol of N2, CH4, H2 at 300K, CO2 at 313K

16