Peng 

Zhang
Monday, Wednesday & Friday 10:10‐
11:05 am
 Fundamental concepts of
thermodynamics
• Thermodynamics is about describing the
behavior of matter and transformation between
different forms of energy on a macroscopic
scale
• Bulk properties
 Units
• Kelvin vs. Celcius

• 1 atm = 101,325 Pa

• Ideal gas constant, R

= 8.314 J/(Kꞏmol)
= 0.08206 (Lꞏatm)/(Kꞏmol)
 Some important terms
• Internal energy, U
• Heat, q
• Work, w
• Isothermal – constant T
• Isobaric – constant P
• Isochoric – constant V
 Some important terms

• System vs. surroundings

• Open vs. closed system (matter exchange)
• Isolated system (no matter nor energy exchange)
• System variables (P, V, T, n)
• Intensive vs. extensive variables
 Some important terms (cont)

• Thermodynamic equilibrium: With respect to P, T,

V/n. No change vs. time
• Thermal equilibrium – same T
• Adiabatic vs. diathermal
 Some important terms (cont)
• State functions vs. path functions
• Reversibility
• Quasi-static process: Rate of change of macroscopic
variables is negligibly small. The system passes
through a succession of states of internal equilibrium
as it goes from initial to final state
• Maximum work that can be extracted from a process
between two states is that obtained under reversible
conditions
 Some important terms (cont)
• Sign of w: Positive means work done to system
• Types of work:
• Volume expansion w = -∫PextdV
• Surface expansion w = -∫γdσ
• Stretching w = -∫Fdl
• Electrical w = ∫ФdQ

• Sign of q: Positive means heat flows to system

 Ideal gas law
• PV = nRT or PVm = RT

• Molecules treated as points (no volume)

• Assuming no interaction between molecules
 Real gas
• Considering volumes of molecules
• Considering interaction between molecules

• van der Waals equation of state:

• P = RT/(Vm-b) - a/Vm2
• a and b are determined experimentally
 Real gas (cont)
• Virial equation of state:
• P = RT[1/Vm + B(T)/Vm2 + …]

• Compression factor, z = PVm/RT

• z = 1 for ideal gas; z ≠ 1 for real gas
 Zeroth law of thermodynamics
• Two systems separately in thermal equilibrium with a
third system are also in thermal equilibrium with one
another.

If T1 = T2 and T2 = T3, then T1 = T3

 First law of thermodynamics
• First law: U of an isolated system is constant,
i.e., ΔUisolated = 0

• ΔUisolated = ΔUsystem + ΔUsurroundings = 0

• ΔUsystem = -ΔUsurroundings

• ΔU = q + w
 Heat capacity
• Measure of the amount of heat needed to change the
temperature of a substance by a given amount

• C = dq/dT, extensive variable

• Molar heat capacity Cm, intensive variable

• Cp vs. Cv
• Cp,m -> 0 as T -> 0
• qp = ∫ Cp(T)dT
• For ideal gas, Cp - Cv = nR or Cp,m – Cv,m = R
 Some important terms (cont)
• Enthalpy H = U + PV, state function
• ΔU for a process involving only P-V work can be
determined by measuring the heat flow at constant
volume, ΔU = qv= Cv(T2-T1)
• ΔH for a process involving only P-V work can be
determined by measuring the heat flow at constant
pressure, ΔH = qp= Cp(T2-T1)
• For an ideal gas, U and H depend on T only