Chap. 2: Thermodynamics 2.2: P-V Work 2.3: Heat 2.4: The 1st Law of Thermodynamics 2.5: Enthalpy 2.

6: Heat Capacities 2.7: The Joule and Joule-Thomson Experiments 2.8: Perfect Gases and the 1st Law 2.9: Calculation of 1st Law Quantities

2.2: P-V Work

1. Work:

dW
Expansion

F dx

2. P-V Work:

F = PA

dV
dx

A dx

dWsys

F dx

PA dx

P A dx

PdV

For a reversible process in a closed system:

dWrev Wrev
1

P(V ) dV
2

Equ-2.26*

P(V ) dV

A reversible process is one where the system is always infinitesimally close to equilibrium, and an infinitesimal change in conditions can reverse the process to restore both system and surroundings to their initial states.

For an isobaric process, P is a constant, then:

Wrev Wrev

2 1

PdV

P 1 dV

P V

3. Line Integrals: See Fig-2.3 on p. 44. The P-V work is path dependent and it is not a state function. Be careful of this!

 Exp-2.2 on p. 44: P-V work

Find the work Wrev for processes (a) and (b) of Fig-2.3 if: P1 = 3.00 atm, V1 = 500 cm3, P2 = 1.00 atm, V2 = 2000 cm3. Also, find Wrev for the reverse of process (a). 1) Wrev for the process (a): This process can be splitted into two sub-processes: [a,1] from the initial point, 1, to the turning point. [a,2] from the turning point to the ending point, 2.

Note: [a,1] is an isochoric process and [a,2] is an isobaric process.

Because Wrev

2 1

P(V ) dV and dV = 0 for [a,1], we

obtain: Wrev,[a,1] 0. However, Wrev,[a,2] 0 in that

[a,2] is an isobaric process. For this change:

Wrev, a , 2 Wrev, a , 2 P V P V2 V1 101325 Pa 2000. 10 6 m3 500. 10 6 m3

Wrev, a , 2 152J Wrev,[a] = Wrev,[a,1] + Wrev,[a,2] = 0 + (-152J) = -152 J

Similarly, for the reverse process (a): Vinitial = V2, Vfinal =

V1, and Pinitial = P2, and Pfinal = P1. Use these relations we
can get Wrev,[-a] = +152 J for the reverse process (a).

2) Wrev for the process (b):

Process (b) is very similar to process (a) except that: [b,1] is an isobaric expansion process, and

[b,2] is an isochoric process.

Thus, Wrev,[b] = Wrev,[b,1] + Wrev,[b,2] Wrev,[b] = -P1(V2 V1) + 0 Wrev,[b] = -(3 101325 Pa)(2000. 500.) 10-6 m3 Wrev,[b] = -456J

4. Irreversible P-V work:

The work W in a mechanically irreversible volume change sometimes cannot be calculated with thermodynamics. According to the Law of The Conservation of Energy:

dwirrev

Pexternal dV dKpiston

It is very hard to figure out the change of the kinetic energy of the piston, Kpiston, during its acceleration. However, if we wait longer enough, kpiston 0. We then have: 2

Wrev

Pexternal dV

2.3: Heat
Heat is a means of energy transfer due to the temperature difference between two objects. dq Heat Capacity: C dT dq c Specific Heat Capacity: dq mdT ~ c Molar Heat Capacity: ndT Calorimetric Method: dqin = dqout T dq = mcdT q m T cP T dT Calorie (cal): The amount of heat needed to raise one gram of water from 14.5 C to 15.5 C at 1 atm pressure.
2 1

2.4: The 1st Law of Thermodynamics

E=K+V+U
E: The energy of a body
K: Kinetic energy V: Potential energy U: Internal energy

If focus on thermodynamics: let K = 0, V =0,

then, E = U Molar Internal Energy: Um = U/n The 1st Law of Thermodynamics: U = q + w for closed system, at rest, no fields.

 For an infinitesimal process:

dU = dq + dw (for closed systems)

U 0 for a cyclic process.

Equ-2.40*

Example 2.3 on p. 50: Calculation of U

Calculate U when 1.00 mol of H2O goes from 25.0 C

and 1.00 atm to 30.0 C and 1.00 atm.

Note: U is a state function. You can always choose your

favorite path to do the calculation.

U = q + w, figure out q and w separately and then

calculate the U.

2.5: Enthalpy
Enthalpy, H U + PV
Why we define enthalpy, H?

Equ-2.45*

q U

q H

Expansion

Fixed V but P increases

Fixed P but V increases

Note: H = qP , U = qV (Equ-2.46*/2.49*, p. 52)

 At fixed pressure:

H = (U + PV) = U + (PV) = U + PV For solids and liquids, V is very small when

temperature changes (incompressible), thus:

H U (for solids and liquids)

For gases, V changes a lot when temperature

changes, the PV term cannot be overlooked, thus: H U (for gases)

2.6: Heat Capacities

For an infinitesimal process: C pr

dq pr dT

For a closed system, we can define two types of capacities:

Heat capacity at constant pressure:

CP

dqP dT dqV dT

H dT U dT

H T U T

Heat capacity at constant volume:

CV

 CP(T, P) and CV(T,V) H(T,P) and U(T,V) Molar Heat Capacity:

C P .m CP n ~ CP
H T U U T U T

CV .m

The relations between CP and CV

C P CV C P CV C P CV
P V

CV n

~ CV

PV T P
P

U T

V T

U T

 How do we figure out

dU U T U T U T dT
V

U T

U T

?
V

U V

dV
T

At the constant pressure P : dU P dU P dTP UP TP dTP

V

U V U V

dVP
T

dVP dTP V T

U T

U V

Thus

C P CV

U V

P
T

V T

2.7: The Joule & Joule-Thomson Experiment

1. Joule Experiment (1843): Try to find
U V
T

See Fig-2.6 on p. 55.

Actually, the Joule Experiment measures the

T change with change in V at constant U.

From the experiment, we can measure the

Joule Coefficient:
J

T V
U V
T

Equ-2.62
U

How could we obtain

from J?

Apply Eulers Chain Rule to U(T,V)!

 Because

U V T
V U U T 1
T

U T
Thus

T V

U V

T V

CV
U

2. Joule-Thomson Experiment (1853): See Fig-2.7 on p. 56.

H P

The Joule-Thomson Experiment measures

the T change with change in P at constant H.

From the experiment, we can measure the

Joule-Thomson Coefficient:

Equ-2.64*
How could we obtain

T JT P H from J?
P
T

Apply Eulers Chain Rule to H(T,P)!

 Because

H P T
P H H T 1
T

H T
Thus

T P

H P

T P

CP
H

JT

2.8: Perfect Gases and The 1st Law

1. Perfect Gas: see Eq-2.66*, Eq-2.69*, Eq-2.70*
PV nRT and U V 0
T

This implies: U = U(T) U only depends on

T for perfect gases.

Since CV
U T

, at constant V, this equation

V

becomes an ordinary derivative, CV

Thus, dU Cv dT . Similarly, dH
CP dT .

dU dT

 Combine Eq-2.61* with Eq-2.66*:

C P CV PV nRT U V P
T

V T

Since

U V

0 , CP CV
T

V T

nR
P

Therefore, for perfect gases: CP,m CV,m = R U H 0, CV 0; 0, CP 0 0, JT 0 J V T P T The 1st Law for perfect gases:

dU = CVdT = dq + dw = dq - pdV

Example 2.4, p. 59: Calculation of q, w and U Suppose 0.100 mol if a perfect gas having CV,m = 1.50R independent of temperature undergoes the reversible cyclic process 1 2 3 4 1 shown in Fig-2.10, where either P or V is held constant in each step. Calculate q, w, and U for each step and for the complete cycle. Solution: see p. 59

2. Reversible Isothermal Process in a Perfect Gas

Isothermal dU = 0, thus dq = -dw

Because dw = -pdV, dq = pdV

Ideal gas: PV = nRT, thus, P = nRT/V
W W W q
V2 V1 V2 V1 V2
1

PdV

nRT dV V

nRT

V2 V1

dV V

nRT lnV V V1 nRT ln V2 W

nRT ln V2 ln V1 P2 nRT ln P 1 P nRT ln 1 P2

V2 nRT ln V1

Example 2.5 on p. 60. A cylinder fitted with a frictionless piston contains 3.00 mol of He gas at P = 1.00 atm and is in a large constant-T bath at 400 K. The pressure is reversibly increased to 5.00 atm. Find q, w, and U for this process. For an isothermal process, U = 0, q = -w
w
V2 V1

PdV

T2 T1

nRT dV V

V2 nRT ln V1

P2 nRT ln P 1

3. Reversible Constant-P (or Constant-V) Process in a Perfect Gas: See Example 2.4!

4. Reversible Adiabatic Process in a Perfect Gas

For an adiabatic process: dq 0

For a reversible process with only P-V work:

dw = -PdV

For a perfect gas: dU = CVdT

Thus, the 1st law becomes: CVdT = -PdV

For an ideal gas: P = nRT/V = RT/(V/n) = RT/Vm

Then we get:
CV ,m dT Cv , m dT T RT dV V dV R V

1 CV ,m dT T1 T T CV ,m ln 2 T1
T2 R

1 dV V1 V V V R ln 2 R ln 1 V1 V2 R
V2

T2 T1

V1 V2

CV ,m

PV1 For a perfect gas, 1 T1

R

P2V2 T2 P2V2
1

T2 T1
R CV ,m

P2V2 PV1 1 PV1 1

1
R CV ,m

PV Hence, 2 2 PV1 1

V1
R

CV ,m CV ,m

V2

Note : C P ,m CV ,m Define C P ,m CV ,m

R R, thus, 1 CV ,m P2V2

C P ,m CV ,m

, we get : PV1 1

For an adiabatic process, U = q + w = w. Since U = CVT and CV is a constant for a perfect gas

U = CV(T2 T1) = w
This formula is applied to a perfect gas, reversible adiabatic process, and a constant CV.

See Fig-2.12 on p. 61.

2.9: Calculation of 1st Law Quantities

Thermodynamic Processes

T = P = V = U = H = 0 Reversible: dwrev = -PdV infinity small process Isothermal: T is constant throughout the process Adiabatic: dq 0, q 0 Constant-V: dV 0, V 0, U = qV (Isochoric Change) Constant-P: dP 0, P 0, H = qP (Isobaric Change)
Cyclic:

 The q, w, U, H for various process: 1. Reversible phase change at const. T and P A Phase change or phase transition 2. Const.-P heating with no phase change

w wrev H qP

2 1 T2 T1

PdV

P V

CP T dT at const. P

3. Const.-V heating with no phase change

U H

qV U

T2 T1

CV T dT at const.V U PV U V P

PV

4. Perfect gas change of state T2 T2 U CV T dT H C P T dT T1 T1 5. Reversible isothermal process in a perfect gas

q w 0 implies qV
2 1

0 or qP V2 nRT ln V1

0, thus U q

0, H

PdV

V2 w nRT ln V1

6. Reversible adiabatic process in a perfect gas q 0 implies U w PV1 P2V2 1 7. Adiabatic Expansion of a perfect gas into vacuum q = 0 (adiabatic process) w = 0 (w = -PdV, P = 0 for vacuum surroundings) U = q + w = 0, H = U + (PV) = U + nRT = 0

 Example 2.6: Calculation of H

CP, m of a certain substance in the temperature range 250 K to 500 K at 1 bar pressure is given by CP, m = b + kT, where b and k are certain known constants. If n moles of this substance is heated from T1 to T2 at 1 bar (where T1 and T2 are in the range 250 K to 500 K), find the expression for H.
H H
T2 T1

nC P ,m dT

T2 T1

b kT dT

n bT

1 2

kT 2

T2 T1

n b T2 T1

1 k T22 T12 2