FORMULAS FOR THERMODYNAMICS 1

MEASURES OF AMOUNT OF SIZE FIRST LAW OF THERMODYNAMICS

Specific volume = Esystem + Esurroundings = 0
Esurroundings = Q W
Molar volume, Vm =
Esystem = U + PE + KE
Q W = U + PE + KE
FORCE
1 For closed systems: (PE and KE are constant)
=
E = U = Q + W
For finite changes: U = Q + W
PRESSURE For differential changes: dU = dQ + dW

= =
Enthalpy:
H = U + PV
WORK For finite changes: H = U + (PV); H = U + VP +
= U PV
For differential changes: dH = dU + d(PV)
ENERGY For constant pressure process: H = U + PV
a. Kinetic energy
1 2 Heat Capacity:
= 2 =
2 2 Constant pressure: Q = H = nCpT
b. Potential energy Constant volume: Q = U = nCvT

= =
MATERIALS & ENERGY BALANCES FOR OPEN SYSTEMS
1u1A1 = 2u2A2 (continuity equation)

OVERALL ENERGY BALANCE EQUATION

2
W + Q = Z + 2 + H

EQUATIONS FOR PROCESS CALCULATIONS: IDEAL GAS

(Mechanically Reversible Closed-System Processes)
Q U H W
Isochoric U nCvT nCpT 0
Isobaric nCvT nCpT U - Q

Isothermal -W 0 0 RT 1 = RT 2
2 1
Adiabatic 0 nCvT nCpT U
 EQUATIONS OF STATE
Virial Equations
1. Application of virial equations

= = 1 + where B 2nd virial coefficient (equation 1)

= =1+ truncated in two terms (equation 2)


=
=1+ + 2
truncated in three terms (equation 3)

2. Extended virial equation: Benedict/Webb/Rubin Equation

0 0 0 / 2 2
= + 2
+ 3
+ 6 + 3 2 (1 + 2 ) /

3. Cubic equations of state

a. Van der Waals Equation of state

= 2

272 2
Where = =
64 8

b. Vapor & vapor-like roots of the generic cubic equation of state

()
= + [ ]
( )( + )

For Z: = 1 +
(+)(+)

= =

c. Vapor & vapor-like roots of the generic cubic equation of state

+
= + ( + )( + ) [ ]

For Z:
1+
= + ( + )( + ) [ ]

d. Other equations: Soave/Redlich/Kwong SRK Equation and Peng Robinson PR
Equation

Equation of
Tr Zc
state
VDW 1 0 0 1/8 27/64 3/8
RK Tr1/2 1 0 0.08664 0.42748 1/8
SRK SRK 1 0 0.08664 0.42748 1/8
PR PR 1 + 2 1 2 0.07779 0.45724 0.3074
1/2 2
= [1 + (0.480 + 1.574 0.1762 ) (1 )]
1/2 2
= [1 + (0.37464 + 1.5422 0.269922 ) (1 )]