CHEE 220 Formula Sheet

First law of Thermodynamics:

ΔU = Q + W dU = dQ + dW
Second law of Thermodynamics:
dQrev dQrev
ΔS = ∫ T
dS =
T
Enthalpy
ΔH = ΔU + ΔPV
Free Energies

ΔG = ΔH − TΔS
Heat Capacities
" ∂U % " ∂H %
$ ' = CV $ ' = CP
# ∂T &V # ∂T &P
Fundamental Thermodynamic Relations for closed systems

Fundamental Gibbs Energy Relation for an open or reacting system

Maxwell equations

Expansion Work
dW = −PdV
Residual and Excess Properties

M = M ig + M R M = M id + M E
Expressions for Internal Energy
"β %
dU = CV dT + $ T − P' dV
#κ &
Ideal Gas
dU = CV dT

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Expressions for Enthalpy

dH = C p dT + (1− β T )VdP
Ideal Gas:
dH = C p dT
Residual Enthalpy Calculations:

Expressions for Entropy

Ideal Gas:

Residual Entropy Calculations:

Residual Gibbs Energy

P
GR (Z −1)
RT
= ∫ P
dP
0

Clapeyron Equation Clausius-Clapeyron Equation

Antoine Equation
B
ln P sat = A −
T +C

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Mole Fractions

n n liq n vap Ln + Vn = 1
zi = i
n
∑
zi = 1 Ln =
n
Vn =
n
General VLE equations
^ ^
α β µiα = µiβ ,
T =T ,
α
P =P β
,
α
f =f
i i
β

^
φi yi P = γ i xi fi
Modified Raoult’s law

yi P = γ i xi P isat
Raoult’s law Henry’s Law

Saturation Pressures of Multicomponant Systems

P = ∑γ i xi Pi sat 1
P=
y
i
∑ γ Pisat
i i i
Shortcut Equations for Saturation Pressures for Ideal Binary Mixtures

Liquid and Vapor fractions

Azeotropes

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CHEE 220 Formula Sheet

Total differential of Molar Properties and Partial Molar Properties

" ∂(nM ) $ " ∂(nM ) $ " ∂(nM ) $

d(nM ) = " $ dP + " $ dT + ∑" $ dni
# ∂P %T ,n # ∂T %P,n i # ∂ni %P,T ,nj
,

Summability of Partial Molar Properties

,
Gibbs Duhem
General Binary
d M1 d M2
x1 + x2 =0
dx1 dx1
Rationale for Parial Molar Properties

Partial Molar Properties of binary Mixtures

Chemical Potential

System property summability

Gibbs Theorem

M iig (T, P) = M iig (T, Pi* )

Ideal Gas Model

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Fugacity

GiR = RT ln φi
, ,
^
R
, ,
G = RT ln φi
i

Fugacity of Pure Fluids

Ideal Gas Real Gases Pure Liquids in VLE

, ,
Fugacity of mixtures and solutions
Ideal Gas Ideal Solution of Gases Real Gas Mixtures

, ,
Ideal liquid solutions Real liquid solutions

, , ,
Fugacity calculations from PVT
Pure species
" V sat (P − Pi sat ) %
fi l = φisat Pi sat exp $ i,l '
, , # RT &
In mixtures

,
^
P ^
P
ln φ1 =
RT
( B11 + y2
2
(2B12 − B11 − B22 )
) ln φ 2 =
RT
(
B22 + y12 (2B12 − B11 − B22 ) )

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CHEE 220 Formula Sheet

Ideal Solution Model Summary

ΔVmix = 0 ΔH mix = 0

Excess Gibbs Energy as a model for activity coefficients

Experimental activity coefficients

Single term Redlich Kister

GE
= Ax1 x2 ln γ1 = Ax22
RT
Margules Fit Function

Van Laar Fit Function

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CHEE 220 Formula Sheet

Thermodynamic Consistency
γ1 d ln γ1* d ln γ 2* γ1 γ1mod γ1exp
δ ln = x1 + x2 δ ln = ln mod − ln exp
γ2 dx1 dx1 γ2 γ2 γ2

Sensible Heat Effects

Relations for Ideal Gases

Latent Heat
Ridel Equation Watson Equation
0.38
ΔH 2 # 1− Tr 2 &
=% (
ΔH n 1.092(ln Pc (bar) −1.013) ΔH1 $ 1− Tr1 '
=
RTn 0.930 − Tr.n
Chemical Reactions
ν1 1 A1 + ν 2 1 A2 +... !!
→ ν 3 1 A3 + ν 4 1 A4 +...
ν1 j A1 + ν 2 j
A2 +... !!
→ ν3 j
A3 + ν 4 j
A4 +...

ni = ni,0 + ∑ν i, jε j
j

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Chemical Potential criteria for Chemical Reactions

The Standard Gibbs Energy and the Equilibrium Constant

Dependence of the Equilibrium constant on Temperature

Standard Properties of reaction

Depence on Temperature of the Enthalpy of reaction

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The equilibrium constant and compositions

General Equilibrium constant definition
v
" ^ %i
K = ∏ $ fi o '
i $ fi '
# &
General Gas Phase reactions Ideal Solution of gasses

Ideal Gas

Real Liquid Mixtures Ideal Solutions

Dilute Solution Reactions (infinite dilution) Real dilute solutions

vi
K = ∏m i "^ % i
v
v
K = ∏ $ a i ' = ∏ (γ i,m mi ) i
i i # & i

Statistical Thermodynamics
Weight of a configuration Maxwell-Boltzmann Distribution
N! ni e− βεi 1
W= =
∏ ni ! − βεi β =
N ∑e , kT
i i
The statistical Entropy
S = k lnW
Equations of State
General Correlations
dV 1 " ∂V % 1 # ∂V &
= β dT − κ dP β= $ ' κ =− % (
V V # ∂T &P V $ ∂P 'T
Ideal gas, Z=1
Virial Equation
BP
Z = 1+
RT
Van der Waals

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Redlich – Kwong

Pitzer Method
Pr 0.172
Z = 1+ ( B 0 + ω B1 ) B1 = 0.139 −
Tr T r4.2
dB 0 0.675 dB1 0.722
= 2.6 = 5.2
dTr Tr dTr Tr
Multicomponant
ωi + ω j
ωij = T = (T T )1/2
(1− kij ) ! 13 1 $ 3

2 cij ci cj
Vcij = # Vci + Vcj 3 &
# 2 &
" %
Z cij RTcij Z +Z
Pcij = Z cij = ci cj
Vcij 2
0.172
RT Bijo = 0.083 −
0.422 Bij1 = 0.139 − 4.2
Bij = (Bij0 + ω ij Bij1 ) cij T 1.6
rij
T rij
Pcij
Rackett Equation
0.2857
Vl sat = V c Z c(1−Tr )
Corresponding states

Phase Rule Duhem’s Theorem

F = 2−Π+C −r −s F=2
Total Differential
For Total Differential
# ∂F & # ∂F &
dF ≡ % ( dx + % ( dy
F(x, y) $ ∂x 'y $ ∂y 'x
If
# ∂F & # ∂F &
dF = Mdx + Ndy M ≡% (
$ ∂x 'y
,
N ≡% (
$ ∂y 'x
R : 8.314 J.mol-1.K- 1 bar = 1x105 Pa

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