Real Gases

 Correction factor PV=ZnRT

𝑉 𝑉 𝑃𝑉
𝑍= = 𝑛𝑅𝑇 =
𝑉𝑖𝑑𝑒𝑎𝑙 𝑛𝑅𝑇
Compressibility  Pro:
𝑃

Factor  Easy to use

Z  Con:
 Z varies with temperature
and pressure, and is
different for each substance
  Compressibility Factor
PV=ZnRT

 Virial
𝐵(𝑇) 𝐶(𝑇) 𝐷(𝑇)
𝑃𝑉𝑚 = 𝑅𝑇 1 + + + +⋯
𝑉𝑚 𝑉𝑚 2 𝑉𝑚 3
Equations of  Berthelot
𝑅𝑇 𝑎
State for Real 𝑃= −
𝑉𝑚 − 𝑏 𝑇𝑉𝑚 2
Gases  Dieterici 𝑎
−
𝑅𝑇𝑒 𝑚𝑅𝑇
𝑉
𝑃=
𝑉𝑚 − 𝑏
 Van der Waals
 Corresponding States
 𝑎
 𝑃+𝑉 2 𝑉𝑚 − 𝑏 = 𝑅𝑇
𝑚
𝑛2 𝑎
 𝑃+ 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉2
 Pros:
 Physical meaning
Van der Waals  a and b depend on the substance, but don`t vary with T or P
Equation  Predicts liquid-vapor equilibrium

 Cons:
 Not AS easy to use as ideal gas law
 Depends on a and b

𝑃𝑉𝑚 3 + −𝑃𝑏 − 𝑅𝑇 𝑉𝑚 2 + 𝑎𝑉𝑚 − 𝑎𝑏 = 0

Phase Diagrams and Critical Point
Critical Point Van der Waals Equation
 𝑎
𝑃+𝑉 2 𝑉𝑚 − 𝑏 = 𝑅𝑇
𝑚
𝑅𝑇 𝑎 𝑅𝑇𝑐 𝑎
𝑃=𝑉 −𝑉 2 𝑃𝑐 = 𝑉 −𝑉 2
𝑚 −𝑏 𝑚 𝑚𝑐 −𝑏 𝑚𝑐
𝜕𝑃 𝑅𝑇 2𝑎 𝑅𝑇𝑐 2𝑎
=− +𝑉 3 0=− +𝑉 3
𝜕𝑉𝑚 𝑇 𝑉𝑚 −𝑏 2 𝑚 𝑉𝑚𝑐 −𝑏 2 𝑚𝑐

𝜕2 𝑃 2𝑅𝑇 6𝑎 2𝑅𝑇𝑐 6𝑎
= −𝑉 0= −𝑉
𝜕𝑉𝑚 2 𝑇 𝑉𝑚 −𝑏 3 𝑚
4 𝑉𝑚𝑐 −𝑏 3 𝑚𝑐
4

Critical Point 𝑅𝑇𝑐

𝑉𝑚𝑐 −𝑏 2
=𝑉
2𝑎
𝑚𝑐
3
6𝑎
𝑉𝑚𝑐 4
=
2𝑅𝑇𝑐
𝑉𝑚𝑐 −𝑏 3
𝑅𝑇𝑐 𝑎 𝑎 2𝑅𝑇𝑐 𝑉𝑚𝑐
2 𝑉𝑚𝑐 −𝑏 2
=𝑉 3 𝑉𝑚𝑐 3
=6 𝑉𝑚𝑐 −𝑏 3
𝑚𝑐
𝑅𝑇𝑐 2𝑅𝑇𝑐 𝑉𝑚𝑐
=
2 𝑉𝑚𝑐 −𝑏 2 6 𝑉𝑚𝑐 −𝑏 3
6 𝑉𝑚𝑐 −𝑏 3 2𝑅𝑇𝑐 𝑉𝑚𝑐
=
2 𝑉𝑚𝑐 −𝑏 2 𝑅𝑇𝑐
 3 𝑉𝑚𝑐 − 𝑏 = 2𝑉𝑚𝑐
3𝑉𝑚𝑐 − 3𝑏 = 2𝑉𝑚𝑐 𝑅𝑇𝑐 𝑎
𝑃𝑐 = 𝑉 −𝑉 2
𝑚𝑐 −𝑏 𝑚𝑐
3𝑉𝑚𝑐 − 2𝑉𝑚𝑐 = 3𝑏 8𝑎
𝑅 𝑎
27𝑅𝑏
𝑉𝑚𝑐 = 3b 𝑃𝑐 = − (3b)2
3b−𝑏
𝑅𝑇𝑐 2𝑎
Critical Point 0=− 3𝑏−𝑏 2
+ (3𝑏)3 8𝑅𝑎
𝑃𝑐 = 2b(27𝑅𝑏) − 9𝑏2
𝑎

𝑅𝑇𝑐 2𝑎 4𝑎 𝑎 4𝑎−3𝑎
= 𝑃𝑐 = 27𝑏2 − 9𝑏2 =
4𝑏 2 27𝑏 3 27𝑏 2
2𝑎(4𝑏 2 ) 𝑎
𝑇𝑐 = 𝑃𝑐 = 27𝑏2
𝑅27𝑏 3
8𝑎
𝑇𝑐 = 27𝑅𝑏
 8𝑃𝑐 𝑉𝑚𝑐 2
𝑇𝑐 = 3𝑅𝑉𝑚𝑐
𝑉𝑚𝑐 = 3b 8𝑃𝑐 𝑉𝑚𝑐
𝑅=
𝑏=
𝑉𝑚𝑐
BUT we prefer 3𝑇𝑐
3
not to have Vmc 3𝑅𝑇𝑐 = 8𝑃𝑐 𝑉𝑚𝑐
𝑎 3
𝑃𝑐 = 27𝑏2 𝑃𝑐 𝑉𝑚𝑐 = 8 𝑅𝑇𝑐
𝑉𝑚𝑐 2
Van der Waals 𝑎 = 27𝑃𝑐 𝑏 = 2
27𝑃𝑐 9 PVm=ZRT
3
2 𝑍𝑐 = 8 for all gases?
𝑎 = 3𝑃𝑐 𝑉𝑚𝑐
Could we find an equation
8𝑎
𝑇𝑐 = of state that uses the
27𝑅𝑏
critical point as reference
8(3𝑃𝑐 𝑉𝑚𝑐 2 )
𝑇𝑐 = 𝑉
instead of constants like
27𝑅 𝑚𝑐 a, b or Z?
3

We’ll get to it, now back

to…
 We got a and b from the
3
𝑃𝑐 𝑉𝑚𝑐 = 𝑅𝑇𝑐 critical values (no
8 volume). ☺
3𝑅𝑇𝑐
𝑉𝑚𝑐 = = 3𝑏 So back to the idea of
8𝑃𝑐
𝑅𝑇
finding an equation using
𝑏 = 8𝑃𝑐 the critical point as
Van der Waals 𝑐
𝑎 = 3𝑃𝑐 𝑉𝑚𝑐 2 reference.
3𝑅𝑇𝑐 2 We’ll start defining
𝑎 = 3𝑃𝑐 reduced properties.
8𝑃𝑐
27𝑅2 𝑇𝑐 2 𝑇 𝑃
𝑎= 𝑇𝑟 = 𝑇 𝑃𝑟 = 𝑃
64𝑃𝑐 𝑐 𝑐
𝑉𝑚
𝑉𝑚𝑟 = 𝑉𝑚𝑐
 𝑅𝑇 𝑎
𝑃=𝑉 −𝑉 2
𝑚 −𝑏 𝑚
8𝑃𝑐 𝑉𝑚𝑐 Pros:
𝑇 3𝑃𝑐 𝑉𝑚𝑐 2
3𝑇𝑐
𝑃= −  No constants that depend
𝑉
𝑉𝑚 − 𝑚𝑐 𝑉𝑚 2
3
8𝑉𝑚𝑐 𝑇
on the substance.
𝑃 3 𝑇𝑐 𝑉𝑚𝑐 2
= 3𝑉𝑚−𝑉𝑚𝑐 −3  Critical point is the only
𝑃𝑐 𝑉𝑚
3 reference.
Corresponding 8𝑉𝑚𝑐 𝑇𝑟 1 2
𝑃𝑟 = −3 Con:
States Equation 3𝑉𝑚 −𝑉𝑚𝑐 𝑉𝑚𝑟
8𝑇𝑟 3  Cubic equation (not as easy)
𝑃𝑟 = −
3𝑉𝑚 −𝑉𝑚𝑐 𝑉𝑚𝑟 2
𝑉𝑚𝑐 Can we find an equation as
8𝑇𝑟 3 easy to use as ideal gas BUT
𝑃𝑟 = 3𝑉𝑚 𝑉𝑚𝑐 − with the advantages of
− 𝑉𝑚𝑟 2
𝑉𝑚𝑐 𝑉𝑚𝑐
corresponding states?
8𝑇𝑟 3
𝑃𝑟 = 3𝑉 −𝑉 2
𝑚𝑟 −1 𝑚𝑟
Corresponding
States
How real is it?
Z=Vreal/Videal
Compressibility Factor
Diagram

 Example:
 For helium, Pc=0.229MPa and
Tc=5.25K. Find the volume
occupied by 3 moles of helium
at 5.775K and 0.458 MPa.

 0.1257L
  Calculus states that given Z=Z(x, y, w) (Z is a function that
depends on x, y and w)
𝜕𝑍 𝜕𝑍 𝜕𝑍
 Then 𝑑𝑍 = 𝑑𝑥 + 𝑑𝑦 + 𝑑𝑤
𝜕𝑥 𝑦,𝑤 𝜕𝑦 𝑥,𝑤 𝜕𝑤 𝑥,𝑦
𝜕𝑍
 Each is a response coefficient and determines how the
𝜕𝑥 𝑦,𝑤
property Z changes when x is modified while y and w remain
Response constant. It is a mathematical expression defining how a system
responds to a controlled stimulus while all other parameters
Coefficients remain unmodified.
 If we multiply the response coefficient by the change applied on
the corresponding variable, we get the effect said change will have
on the state of the system.
 If we add all the effects for all possible modifications, we get the
total effect.
 This math expressions have a real experimental meaning.
  For a gas, we measure α and κ.
1 𝜕𝑉 1 𝜕𝑉𝑚 𝜕𝑉
 ∝= = =∝ 𝑉
𝑉 𝜕𝑇 𝑃 𝑉𝑚 𝜕𝑇 𝑃 𝜕𝑇 𝑃
Response  α is the coefficient of thermal expansion. Usualy positive.
Coefficients  𝜅 = −𝑉
1 𝜕𝑉
= −𝑉
1 𝜕𝑉𝑚 𝜕𝑉
= −𝜅𝑉
𝜕𝑃 𝑇 𝑚 𝜕𝑃 𝑇 𝜕𝑃 𝑇

 κ is the coefficient of isothermal compressibility. Always positive.

 𝜕𝑥 1
 = 𝜕𝑦
𝜕𝑦 𝑧
𝜕𝑥 𝑧

Math Tools
𝜕𝑥 𝜕𝑦 𝜕𝑧
 = −1
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑥 𝑦
 𝜕𝑉 𝜕𝑉
 We know =∝ 𝑉 y = −𝜅𝑉
𝜕𝑇 𝑃 𝜕𝑃 𝑇

 Lets find the other combinations.

𝜕𝑇 1 𝜕𝑃 1
 = and = − 𝜅𝑉
𝜕𝑉 𝑃 𝛼𝑉 𝜕𝑉 𝑇
𝜕𝑉 𝜕𝑇 𝜕𝑃
In the case of a  𝜕𝑇 𝑃 𝜕𝑃 𝑉 𝜕𝑉 𝑇
= −1

gas… 
𝜕𝑇
=− 𝜕𝑉
1
𝜕𝑃 =−
𝜕𝑉
𝜕𝑃 𝑇
𝜕𝑉 =−
−𝜅𝑉
𝜕𝑃 𝑉 ∝𝑉
𝜕𝑇 𝑃 𝜕𝑉 𝑇 𝜕𝑇 𝑃
𝜕𝑇 𝜅 𝜕𝑃 𝛼
 = and =
𝜕𝑃 𝑉 𝛼 𝜕𝑇 𝑉 𝜅

 These response coefficients can be measured through lab

experiments.
  V=V(T,P)
𝜕𝑉 𝜕𝑉
 𝑑𝑉 = 𝜕𝑇 𝑃
𝑑𝑇 + 𝜕𝑃 𝑇
𝑑𝑃

 𝑑𝑉 = 𝛼𝑉𝑑𝑇 − 𝜅𝑉𝑑𝑃
 We measure α and κ at the lab, we substitute and find the integral.
 It can be done starting from T or P.
In the case of a  T=T(V,P)
gas…  𝑑𝑇 =
𝜕𝑇
𝑑𝑉 +
𝜕𝑇 1 𝜅
𝑑𝑃 = 𝛼𝑉 𝑑𝑉 + 𝛼 𝑑𝑃
𝜕𝑉 𝑃 𝜕𝑃 𝑉

 P=P(V,T)
𝜕𝑃 𝜕𝑃 1 𝛼
 𝑑𝑃 = 𝑑𝑉 + 𝑑𝑇 = − 𝜅𝑉 𝑑𝑉 + 𝜅 𝑑𝑇
𝜕𝑉 𝑇 𝜕𝑇 𝑉
 1 1
 For a certain gas, 𝛼 = 𝑇 y 𝜅 = 𝑃 are measured. Find its equation of
state.
𝑉𝑚 𝑉𝑚
𝑑𝑉𝑚 = 𝛼𝑉𝑚 𝑑𝑇 − 𝜅𝑉𝑚 𝑑𝑃 = 𝑑𝑇 − 𝑑𝑃
𝑇 𝑃
𝑑𝑉𝑚 𝑑𝑇 𝑑𝑃
= −
𝑉𝑚 𝑇 𝑃
𝑑𝑉𝑚 𝑑𝑇 𝑑𝑃
Example ‫׬‬ 𝑉𝑚
=‫׬‬
𝑇
−‫׬‬
𝑃

ln 𝑉𝑚 = ln 𝑇 − ln 𝑃 + ln 𝐶
𝑇𝐶
ln 𝑉𝑚 = ln 𝑃
𝑉 𝑇𝐶
=
𝑛 𝑃
PV=nCT
  The state of a paramagnetic solid is described using its
temperature (T), magnetization (M) and the intensity of the
magnetic field (H).
 Response coefficients for a sample of paramagnetic material were
𝜕𝑀 𝐶𝐻 𝜕𝑀 𝐶
measured, and the lab reports 𝜕𝑇 = − 𝑇 2 and 𝜕𝐻 = 𝑇
𝐻 𝑇
where C is a constant. Find the equation of state for this material.
Exercise M=M(T,H)
𝜕𝑀 𝜕𝑀
dM= dT + dH
𝜕𝑇 𝐻 𝜕𝐻 𝑇
𝐶𝐻 𝐶 𝑇𝑑𝐻−𝐻𝑑𝑇 𝐻
𝑑𝑀 = − 𝑇 2 𝑑𝑇 + 𝑇
𝑑𝐻 = 𝐶 𝑇2
= 𝐶𝑑 𝑇
𝐻
𝑀 = 𝐶 𝑇 + 𝑀0
Hint:
𝑌𝑑𝑋 − 𝑋𝑑𝑌 𝑋
= 𝑑
𝑌2 𝑌