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# Thermodynamics

Y Y Shan

 ∂T 

 ∂P  S

2.3. Cooling by isentropic expansion (adiabatic expansion) process: 

It has been pointed out earlier that thermodynamic processes can be mathematically
described by a partial derivative under specific conditions.
“isentropic” above indicates no change of entropy ( dS = 0 , i.e. dQ = 0 ) happened in

the process. “isentropic” process is equivalent to “adiabatic” process (since dS = 0 means
dQ = 0 ).

“expansion” means when volume expands and pressure will change accordingly.
“cooling” means the temperature decreases.
Therefore, cooling by isentropic expansion is dealing with the T~P relationship, or is
aking how temperature changes with respect to the decrease of pressure (when volume
expands) under the isentropic condition?
Thus, the study of “cooling by isentropic expansion” is to answer the following
 ∂T 
questions: 
 =?
 ∂P  S

How does the temperature of a gas change when it expands?

 ∂T 
 :
 ∂P  S

Derivation of 

Entropy S is a state function, for S (T , P ) , mathematically we have
 ∂S 
 ∂S 
dS (T , P) = 
 dT +   dP
 ∂T P
 ∂P T

For isentropic process (constant entropy process), dS = 0 :
 ∂S 
 ∂S 
∴0=
 dT +   dP
 ∂T  P
 ∂P T

thus
 ∂S 
 
 ∂T 
 ∂P T

 =−
 ∂S 
 ∂P  S

 ∂T  P

AP3290

Eq5-6

75

The specific heat  ∂T  P V  ∂T  P  ∂S    = CP / T is the. or  ∂T  P α= 1  ∂V   ∂V    .  ∂P  T  ∂T  P Since the volume expansion coefficient:  ∂S  CP = T   .Thermodynamics Y Y Shan ----------------------------------------------------------------------------------------*Or Eq5-6 can also be obtained directly by applying the “triple product rule”: For S (T . P ) :  ∂S   ∂P   ∂T        = −1  ∂T  P  ∂S T  ∂P  S  ∂S    1 ∂P Therefore:  ∂T  = − = −  T ∂ S ∂ P      ∂S   ∂P  S        ∂T  P  ∂S T  ∂T  P -------------------------------------------------------------------------------------------Applying the Maxwell’s relation (from dG = − SdT + VdP ):  ∂S   ∂V    =-  . or   = αV .  ∂T  P Therefore Eqn5-6 becomes:  ∂S     ∂T   ∂P  T = αTV > 0   =− CP  ∂S   ∂P  S    ∂T  P AP3290 Eq5-7 76 .

. such as a partially opened valve (a throttle) or a porous wall. temperature T will drop. U 2 + P2V2 = U1 + P1V1 . so U 2 − U1 = W 0 V2 V1 0 . This process can be used for gas cooling. AP3290 77 . The throttle valve is well thermally insulated so that no heat is transferred during the process. The gas initially has a pressure P1. After it passes through the valve. W = W1 + W2 = − ∫ P1 dV − ∫ P2 dV = P1V1 − P2V2 so we obtain: U 2 − U1 = P1V1 − P2V2 . Q=0.4.  ∂T    ∂P  H 2. its final pressure is P2 and the volume is V2 The first law for this system can be written as: ∆U = U 2 − U 1 = Q + W Since the system is thermally insulated. i. Joule-Thomson effect(Throttling process): Cooling by isenthalpic expansion  Let us perform a thermodynamic process: a high-pressure gas is forced through a constriction.e.Thermodynamics Y Y Shan Positive slope means that when pressure P decreases (volume expands). temperature T1 and volume V1. It can be concluded that isentropic expansion always causes a decrease in temperature.

In other words. we proceed by starting from the relationship:  ∂P  H µ JT =   ∂S     ∂S    ∂S   ∂S  ∴ dH = T   dT +   dP  + VdP = T   dT + T   + V  dP  ∂P T  ∂T  P  ∂T  P    ∂P T   ∂S   ∂V   ∂S  Applying the Maxwell’s relation:   = . and CP = T   . so    ∂V  CP dT = T   − V  dP   ∂T  P  therefore we obtain the expression for the Joule-Thomson coefficient: AP3290 78 . Given a particular gas and the initial conditions P1 and T1.Thermodynamics Y Y Shan Since the enthalpy is defined as H = U + PV . who together studied this process in the 1850s. which is named after James Joule and William Thomson. we want to know the change of temperature of the gas (from T1 to T2) with respect to the change of its pressure (from P1 to P2) in this isenthalpic process:  ∂T   =?  ∂P  H µ JT =  Eqn5-8 This thermodynamic quantity µJT is known as the Joule-Thomson coefficient.  . so we get H 2 = H 1 or ∆H = H 2 − H 1 = 0 Thus throttling process is a constant enthalpy process (isenthalpic process). we wish to know what the final temperature T2 will be. To find out  ∂T   .  ∂P T  ∂T  P  ∂P  P dH becomes:   ∂V   dH = CP dT + V − T    dP  ∂T  P   For isenthalpic process (constant enthalpy process): dH = 0 . and final pressure P2 .

For any given pressure. →   =  ∂T  P P T µ JT = 0 . the inversion temperature TInv is fairly high (above room temperature). For all real gases. it is straightforward to show that For an ideal gas. For most gases at atmospheric pressure. . when a real gas expands freely at constant enthalpy. throttling expansion causes the temperature to rise ( T2 > T1 ). and so isenthalpic expansion can be applied for gas cooling at those temperature and pressure conditions. depending on the initial temperature ( T1 ) and pressure( P1 ).Thermodynamics  1   ∂V   ∂T   =  −V  T   ∂P  H C P   ∂T  P  µ JT =  Y Y Shan Eqn5-10 nR V  ∂V  = . the temperature of an ideal gas does not change after throttling expansion. µJT will equal zero at some temperature point called the Joule- AP3290 79 . as well as the initial temperature and pressure of the gas before expansion. (i) When initial temperature of the gas T1 > TInv . The value of µJT. representing the change of temperature with respect to a change of pressure. PV = nRT . (ii) When T1 < TInv isenthalpic expansion causes cooling ( T2 < T1 ). a real gas has a Joule-Thomson (Kelvin) inversion temperature TInv . However. the final temperature ( T2 ) may either decrease or increase. depends on the specific gas.

German engineer Carl von Linde(1891–1934). So hydrogen expansion at room temperature is very dangerous. and He). liquefaction. 3. where the coefficient equals zero). N2.the following table explains when the Joule∂P Thomson effect cools or heats a real gas. H2. AP3290 80 . so that extremely low temperature can be achieved. Thus. If the gas temperature is then µJT is since ∂P is thus ∂T must be so the gas below the inversion temperature >0 always “-“ negative cools above the inversion temperature <0 always “-“ positive heats Helium and hydrogen are two gases whose Joule-Thomson inversion temperatures at one atmosphere are very low (e. and low temperature achievement The Joule-Thomson effect is applied in the Linde technique as a standard process in the petrochemical industry.e. From air liquefaction to air separation: with air liquefaction.Thermodynamics Y Y Shan Thomson inversion temperature or inversion point. With that in mind ( µ JT = ∂T ).. where the cooling effect is used to liquefy gases (for the production of liquid O2. It is the temperature where the coefficient changes sign (i. These gases include not only oxygen and nitrogen. about −222 °C for helium). Gas cooling.g. helium and hydrogen will warm when expanded at constant enthalpy at typical room temperatures. the gas pressure decreases. In any gas expansion.. meaning ∂P is always negative ( ∂P < 0 ). but also hydrogen and inert gases .a technology for which the future has only just begun. created the conditions needed to produce pure gases using lowtemperature processes.

corresponds to a point on the inversion curve. where the Joule-Thomson coefficient µ JT = 0 .Thermodynamics Y Y Shan Sketch of the first air liquefaction plant from 1895. the temperature of the gas is lowered to such a temperature that . Gas Inversion temperature TInv Liquefying temperature TLiq At 1atm O2 620oC -183oC N2 352oC -196oC H2 -71oC -253oC Ne -239oC -269oC AP3290 81 . the gas that has been cooled by throttling is used to cool the incoming gas. A gas must be below its inversion temperature to be cooled and liquefied. Consequently. the optimum pressure. after throttling. it becomes partly liquefied. Starting at this pressure and ending at a lower pressure (after expansion). the process produces a large temperature drop. from which to start throttling. Once a gas has been pre-cooled to a temperature lower than the maximum inversion temperature. After successive cooling processes. which after throttling becomes still cooler.