Thermodynamics and Phase Behavior

SI Derived Units and Constants Conservation of Mass

R = 459.67 + °F General Balance Equation
m ⋅ kg J m2 ⋅ kg kg N m2 ⋅ kg J 1
N= = J= = Nm Pa = = W= = Hz = K = 273.15 + °C
s2 m s2 m ⋅ s 2 m2 s3 s s °F = 1.8 °C + 32 𝑑𝜃 Rate of Rate at Which Rate at Which Rate at Which θ can be mass, moles, internal energy, or entropy
= = − +
𝑑𝑡 Change of θ θ Enters System θ Leaves System θ is Generated If θ is conserved quantity, generation term zero
Gas Constant = 8.314x10−6 MPa ⋅ m3 Τmol K Water specific heat capacity = 4.184 kJΤkg K Gas Constant = 8.314 JΤmol K
Mass Balance Equation
Gravitational Constant = 9.806 m/s2 Substance concentration = amountΤvolume specific volume = ρ−1 = m3 Τkg
Rate of Rate at Rate at 𝑑𝑀 𝑑𝑁
Important Definitions and Nomenclature Change = Which Mass − Which Mass = ෍ 𝑀ሶ 𝑘 𝑜𝑟 = ෍ 𝑁ሶ 𝑘 𝑀 𝑡2 − 𝑀 𝑡1 = ෍ 𝛥𝑀𝑘
𝑑𝑡 𝑑𝑡
𝑀 = mass (kg) 𝑁 = number of moles (mol) 𝑈 = internal energy (J) of Mass Flows In Flows Out
Important Definitions
3 𝐺 = Gibbs energy (J)
- Isolated system is not affected by changes in surroundings 𝑉 = volume m 𝑃 = absolute pressure (Pa)
- Adiabatic system is thermally isolated from surroundings 𝐻 = enthalpy J 𝑇 = absolute temperature (K) 𝑄ሶ = heat flow rate JΤs
First Law of Thermodynamics
- Open system: mass can flow in and out of system 𝑆 = entropy JΤK 𝑊 = work done on the system (J) 𝜃መ = property θ per unit mass Energy Balance Heat Capacity
- Closed system: mass cannot flow in and out of system First Law: Energy is Conserved
𝑅 = gas constant 𝑊𝑠 = shaft work done on system (J) 𝜃പ = property θ per mole 𝜕ഫ
𝑈
𝑑 Energy of Rate of Rate of 𝑑𝑈 𝐶𝑉 =
- Steady-state: system properties do not change over time 𝐶𝑉 = constant volume molar heat capacity JΤmol K 𝐶𝑃∗ = ideal gas molar heat capacity = − = 𝑄ሶ + 𝑊ሶ + ෍ 𝑀ሶ 𝑘 𝐻
෡𝑘 𝑜𝑟 ෍ 𝑁ሶ 𝑘 𝐻
ഫ𝑘 𝜕𝑇 𝑉
𝑑𝑡 System Energy In Energy Out 𝑑𝑡
- Isothermal: temperature is constant 𝐶𝑃 = constant pressure molar heat capacity 𝑀ሶ 𝑘 = mass flow rate at location 𝑘
1 Total Total 𝛥𝑈 = 𝑁𝐶𝑉 𝛥𝑇
Enthalpy flow
Pure Substance Phase Behavior 𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 = 𝑀𝑣 2 + 𝑀𝑔ℎ + 𝑈
2
heat flow work
𝜕ഫ
𝐻
Pure Substance Phase Diagram Pressure – Volume Diagram Lever Rule Potential Internal 𝑑𝑉 𝐶𝑃 =
Kinetic 𝑄ሶ = ෍ 𝑄ሶ 𝑘 𝑊ሶ = 𝑊ሶ 𝑠 − 𝑃 𝐻 = 𝑈 + 𝑃𝑉 𝜕𝑇 𝑃
energy energy
Lines correspond
ഫ−ഫ
𝜃 𝜃𝑣
energy 𝑑𝑡
to P-V diagram 𝑥𝐿 = 𝛥𝐻 = 𝑁𝐶𝑃 𝛥𝑇
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 ≈ 𝐼𝑛𝑡𝑒𝑟𝑛𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 Total work = shaft work + expansion work
𝜃𝐿 − ഫ
ഫ 𝜃𝑣
𝑃𝑐 CP
Liquid 𝑥𝐿 + 𝑥𝑣 = 1 Second Law of Thermodynamics Free Energy and Reversibility
Pressure
Pressure

Solid 𝑥𝐿 = liquid phase mole fraction Entropy Balance Second Law: Entropy Free Energy Entropy and Work
CP
𝑥𝑣 = vapor phase mole fraction 𝑑𝑆 𝑄ሶ can be created but For a closed, isothermal, For a closed, constant T & V system
= + ෍ 𝑀ሶ 𝑘 𝑆መ𝑘 + 𝑆𝑔𝑒𝑛
ሶ not destroyed constant volume system
𝑊𝑠 = 𝐴2 − 𝐴1 + 𝑇𝑆𝑔𝑒𝑛
𝜃 and 𝜃෠ can be any
ഫ 𝑑𝑡 𝑇
Vapor ሶ
𝑆𝑔𝑒𝑛 ≥0 𝐴 = 𝑈 − 𝑇𝑆
Two-phase region
extensive property that’s 𝑜𝑟 𝐴 = Helmholtz energy
For a closed, constant T & P system
TP BP been converted to intensive ሶ
DP 𝑑𝑆 𝑄ሶ 𝑆𝑔𝑒𝑛 = 0 if process reversible 𝑊𝑠 = 𝐺2 − 𝐺1 + 𝑇𝑆𝑔𝑒𝑛
= + ෍ 𝑁ሶ 𝑘 𝑆പ𝑘 + 𝑆𝑔𝑒𝑛
ሶ For a closed, isothermal,
Temperature 𝑇𝑐 𝜃෠ − 𝜃෠𝑣 𝑑𝑡 𝑇 At Equilibrium constant pressure system And if process reversible
Specific Volume 𝑤𝐿 =
- Triple point represents P & T at which 3 phases coexist 𝜃෠𝐿 − 𝜃෠𝑣 𝑇 = temp at which heat flow takes place 𝑑𝑆 𝐺 = 𝑈 − 𝑇𝑆 + 𝑃𝑉 𝑊𝑠 = 𝐴2 − 𝐴1 & 𝑊𝑠 = 𝐺2 − 𝐺1
- Bubble point pressure equals the dew point pressure ሶ
- At critical point, liquid and vapor phases are 𝑆𝑔𝑒𝑛 = entropy generated within system 𝑑𝑡
=0 & 𝑆𝑔𝑒𝑛 =0
indistinguishable - P & T are constant during phase changes 𝑤𝐿 + 𝑤𝑣 = 1 𝐺 = 𝐻 − 𝑇𝑆 If entropy generated, more work is
required for a given change of state
- If above the critical point, no phase change occurs - Phases have significantly different properties
𝑤𝐿 = liquid phase mass fraction
Differential Entropy Change Can lose free energy by
- Saturated steam table displays properties along generating entropy 𝑊𝑠 = 𝑊𝑠𝑟𝑒𝑣 + 𝑇𝑆𝑔𝑒𝑛
𝑉෠𝑣 ≠ 𝑉෠𝐿 ෡𝑣 ≠ 𝑈
𝑈 ෡𝐿 ෡𝑣 ≠ 𝐻
𝐻 ෡𝐿 𝑆መ𝑣 ≠ 𝑆መ𝐿 𝑤𝑣 = vapor phase mass fraction For a closed system 𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑜𝑟 𝑑ഫ
𝑈 = 𝑇𝑑പ𝑆 − 𝑃𝑑ഫ
𝑉
saturation line

Ideal Gas Properties Engines Power Cycle Components

Ideal Gas Law Heat Capacity Entropy Fugacity Simple Heat Engine Turbines and Compressors Expansion Valve
𝜕ഫ
𝐻 𝜕 𝑈
ഫ + 𝑅𝑇 𝑓=𝑃 𝜙=1 Joule-Thompson Expansion
𝑃𝑉 = 𝑁𝑅𝑇
𝐶𝑃∗ 𝑇 = = 𝛥പ𝑆 = 𝐶𝑉∗ ln 𝑇2 /𝑇1 + 𝑅 ln 𝑉
ഫ 2 /ഫ
𝑉1 𝑄ሶ 1 Heat 𝑄ሶ 2 High P Low P
𝑍=1
𝜕𝑇 𝜕𝑇 𝑓 = fugacity Turbine
𝛥പ𝑆 = 𝐶𝑃∗ ln 𝑇2 /𝑇1 − 𝑅 ln 𝑃2 /𝑃1 𝑇1 Engine 𝑇2 𝑀ሶ 1 , 𝑁ሶ 1 𝑀ሶ 2 , 𝑁ሶ 2
𝐻 = 𝐶𝑃∗ 𝛥𝑇
𝛥ഫ 𝑈 = 𝐶𝑉∗ 𝛥𝑇
𝛥ഫ 𝜙 = fugacity coefficient High P Low P
𝑍 = compressibility
factor 𝐶𝑃∗ = 𝐶𝑉∗ + 𝑅 𝛥പ𝑆 = 𝑆പ2 − 𝑆പ1 𝜙 = 𝑓Τ𝑃 for all P & T 𝑊ሶ 𝑠 𝑊ሶ 𝑠 Valve
𝑀ሶ 1 , 𝑁ሶ 1 𝑀ሶ 2, 𝑁ሶ 2
Volumetric Equations of State Closed system with steady-state flow
System is open, reversible, adiabatic, System (valve) is open and
and operating at steady-state adiabatic with steady-state flow
Real Gas Law van der Waals Peng-Robinson (1978) Redlich-Kwong-Soave −𝑊ሶ 𝑠 = 𝑄ሶ 1 + 𝑄ሶ 2
𝑅𝑇 𝑎 𝑇 𝑅𝑇 𝑎 𝑇 ෡1 = 𝐻
𝐻 ෡2 𝑜𝑟 𝐻
ഫ1 = 𝐻
ഫ2
𝑃ഫ
𝑉 = 𝑍𝑅𝑇 𝑅𝑇 𝑎 𝑃= −
𝑃= − 2 𝑃= −
𝑉
ഫ−𝑏 𝑉 ഫ 𝑉
ഫ +𝑏 𝑇1 − 𝑇2 Low P High P
𝑉
ഫ−𝑏 𝑉ഫ 𝑉
ഫ−𝑏 𝑉 ഫ 𝑉
ഫ +𝑏 +𝑏 𝑉
ഫ −𝑏 𝑇 −𝑊𝑠 = 𝑄1 − 𝑇2 𝑆𝑔𝑒𝑛 Compressor
𝑉
ഫ 𝑃ഫ
𝑉 𝛼 =1+𝜅 1− 𝑇1
𝑍 = 𝐼𝐺 = 𝑇𝑐 𝑅2 𝑇𝑐2 𝑀ሶ 1 , 𝑁ሶ 1 𝑀ሶ 2 , 𝑁ሶ 2 Evaporators (Boilers) and
𝑉
ഫ 𝑅𝑇 1 𝑅𝑇𝑐 𝑅2 𝑇𝑐2 𝑎 𝑇 = 0.42748 𝛼 𝑇
𝑏= 𝑎 𝑇 = 0.47524 𝛼 𝑇 𝑃𝑐 maximum 𝑇1 − 𝑇2 Condensers (Coolers)
𝑍 𝑇𝑟 , 𝑃𝑟
8 𝑃𝑐 𝑃𝑐 𝑇𝑐 = critical temp
work
−𝑊𝑠 = 𝑄1
𝑇1
𝑊ሶ 𝑠
2 𝑏 = 0.0778𝑅𝑇𝑐 Τ𝑃𝑐 𝑃𝑐 = critical pressure 𝑏 = 0.08664𝑅𝑇𝑐 Τ𝑃𝑐 Condenser
𝑇 𝑃 27 𝑅𝑇𝑐 𝑀ሶ 1 , 𝑁ሶ 1
𝑇𝑟 = 𝑃𝑟 = 𝑎= 𝜅 = 0.48 + 1.574𝜔 − 0.176𝜔2
−𝑊ሶ 𝑠 −𝑊𝑠 𝑇1 − 𝑇2 Turbines and compressors produce the same 𝑀ሶ 2 , 𝑁ሶ 2
𝑇𝑐 𝑃𝑐 64 𝑃𝑐 𝜅 = 0.37464 + 1.54226𝜔 − 0.26992𝜔2 𝜔 = acentric factor efficiency = = = final energy and entropy balances.
2 3
𝑄ሶ 1 𝑄1 𝑇1 𝑄ሶ
If 𝜔 > 0.491 𝜅 = 0.379642 + 1.48503𝜔 − 0.164423𝜔 + 0.16666𝜔
𝑇𝑟 = reduced temp 𝑃𝑟 = reduced pressure
If entropy generated increases, the −𝑊ሶ 𝑠 = 𝑀ሶ 1 𝐻
෡1 − 𝐻
෡2 & 𝑆መ1 = 𝑆መ2
Open system with steady-state flow
Equations of State Cubic Form Work Flow engine’s efficiency decreases
−𝑊ሶ 𝑠 = 𝑁ሶ 1 𝐻 𝑆പ1 = 𝑆പ2 𝑄ሶ = 𝑀ሶ 1 𝐻
෡2 − 𝐻
෡1 𝑜𝑟 𝑁ሶ 1 𝐻
ഫ2 − 𝐻
ഫ1
ഫ1 − 𝐻
ഫ2 &
𝑍 3 + 𝛼𝑍 2 + 𝛽𝑍 + 𝛾 = 0 -Find 𝑇𝑐 , 𝑃𝑐 , and 𝜔
Dimensionless Parameters -Calculate a and b Liquefaction of Gas
van der Redlich-Kwong -Input T & P to calculate A and B
Peng-Robinson 𝑏𝑃
Waals and Soave 𝐵= For all EOS -Determine 𝛼, 𝛽, and 𝛾
Linde Process
𝑅𝑇 Compressors
𝛼 −1 − 𝐵 −1 −1 + 𝐵 2
-Solve cubic equation for Z 5 3
𝛽 𝐴 𝐴 − 𝐵 − 𝐵2 𝐴 − 3𝐵 2 − 2𝐵 𝑎𝑃 For VDW, P-R, and Intercoolers Vapor
𝐴= -the 3 roots: 𝑍𝐿 < 𝑍𝑤𝑟𝑜𝑛𝑔 < 𝑍𝑉 (single or multistage)
Gas

Pressure
𝛾 −𝐴𝐵 −𝐴𝐵 −𝐴𝐵 + 𝐵 2 + 𝐵 3 𝑅𝑇 2 and R-K-S EOS 2 3 4 1’’
𝑍𝑉 = vapor Z-factor Condenser
1’
Departure Functions 1 Throttling 6 Liquefied 1’
Valve Liquid Gas
Departure Definition Enthalpy and Entropy Departure 6 4 5 1
𝑃 𝑉
ഫ
𝐻 ഫ 𝐼𝐺 + 𝐻
ഫ =𝐻 ഫ𝐷 Flash Drum Specific Enthalpy
𝐷
𝜕ഫ
𝑉 1 𝑃 𝜕𝑃
𝐻
ഫ = ඲ 𝑉
ഫ− 𝑑𝑃 𝑑𝑃 = 𝑑 𝑃ഫ
𝑉 − 𝑑ഫ
𝑉 ഫ 𝐷 = 𝑅𝑇 𝑍 − 1 + ඲ 𝑇
𝐻 − 𝑃 𝑑ഫ
𝑉 Total Work for Compression Fraction of Liquid Generated
𝛥𝐻
ഫ = 𝛥ഫ ഫ2𝐷 − 𝐻
𝐻 𝐼𝐺 + 𝐻 ഫ1𝐷 𝜕𝑇 𝑃
𝑉
ഫ 𝑉
ഫ 𝜕𝑇 𝑉
ഫ
𝑃=0 ෡𝑖𝑛 = 𝑤𝐿𝑜𝑢𝑡 𝐻
෡𝐿 + 𝑤𝑣 𝐻
෡𝑣
𝐻 𝐼𝐺
𝛥ഫ = ഫ2𝐼𝐺
𝐻 ഫ1𝐼𝐺
−𝐻
𝑉
ഫ =∞
−𝑊ሶ 𝑠 = 𝑀ሶ 𝐻
෡𝑖𝑛 − 𝐻
෡𝑜𝑢𝑡 & 𝑆መ𝑖𝑛 = 𝑆መ𝑜𝑢𝑡 𝐻 ෡𝑜𝑢𝑡 𝑜𝑟 𝐻
෡𝑖𝑛 = 𝐻
𝑤𝑣 = mass fraction of vapor
𝑃 𝑉
ഫ
van der Waals EOS Total work required for compression ෡3 − 𝐻
𝐻 ෡5 𝐻෡𝑖𝑛 − 𝐻
෡𝑣
𝜕ഫ
𝑉 𝑅 𝜕𝑃 𝑅 𝑤𝐿 = mass fraction of liquid
𝑆പ = 𝑆പ 𝐼𝐺 + 𝑆പ 𝐷 𝐷
𝑆പ = − ඲ − 𝑑𝑃 𝐷
𝑆പ = 𝑅ln𝑍 + ඲ − 𝑑ഫ
𝑉 𝐴 equals the summation of each stage 𝑤𝐿𝑜𝑢𝑡 = =
𝜕𝑇 𝑃 𝜕𝑇 𝑉
ഫ ഫ 𝐷 = 𝑅𝑇 𝑍 − 1 −
𝐻 ෡6 − 𝐻
𝐻 ෡5 𝐻෡𝐿 − 𝐻෡𝑣
𝛥പ𝑆 = 𝛥പ𝑆 𝐼𝐺 + 𝑆പ2𝐷 − 𝑆പ1𝐷
𝑃 𝑉
ഫ 𝑍
𝑃=0 𝑉
ഫ =∞
Power Generation and Refrigeration Cycles
Peng-Robinson Departure Functions
Rankine Cycle Refrigeration Cycle
𝑇 𝑑𝑎Τ𝑑𝑇 − 𝑎 𝑍+ 1+ 2 𝐵 𝑑𝑎 𝑅2 𝑇𝑐2 𝛼 𝑑𝑎Τ𝑑𝑇 𝑍+ 1+ 2 𝐵
ഫ 𝐷 = 𝑅𝑇 𝑍 − 1 +
𝐻 ln = −0.45724 𝜅 𝑆പ 𝐷 = 𝑅ln 𝑍 − 𝐵 + ln High-pressure 𝑄𝐵ሶ High-pressure Low-pressure
𝑄𝐵ሶ
Low-pressure
2𝑏 2 𝑍+ 1− 2 𝐵 𝑑𝑇 𝑃𝑐 𝑇 𝑇𝑐 2𝑏 2 𝑍+ 1− 2 𝐵 Vapor Two phases
Steam Water 1 4
Pressure

3 Boiler 2 3 Boiler 2
Phase Equilibrium and Fugacity Mixtures 𝑊ሶ 𝑠 Compressor
𝑊ሶ 𝑇 𝑊ሶ 𝑃
Turbine Pump Valve
Equilibrium Criteria Fugacity Multicomponent Equilibrium 2 3
Gibbs free energy departure function
Phase I & Phase II 𝑓𝐼 = 𝑓 𝐼𝐼 = 𝑓 𝐼𝐼𝐼 𝑓𝑖ҧ𝐼 = 𝑓𝑖ҧ𝐼𝐼 = 𝑓𝑖ҧ𝐼𝐼𝐼 … 1 Specific Enthalpy
𝑃 4 1 4 Condenser
𝑁 = 𝑁 𝐼 + 𝑁 𝐼𝐼 = constant 𝐺
ഫ−𝐺ഫ 𝐼𝐺 1 𝑅𝑇 𝑓𝑖𝐼ҧ = fugacity of component 𝑖 in phase 𝐼 Condenser Coefficient of Performance
𝑓 = 𝑃 exp = 𝑃 exp න 𝑉
ഫ− 𝑑𝑃 = 𝑃𝑎 Low-pressure Low-pressure High-pressure High-pressure
𝑉 = 𝑉 𝐼 + 𝑉 𝐼𝐼 = constant 𝑅𝑇 𝑅𝑇 𝑃
Steam 𝑄𝐶ሶ Water Vapor 𝑄𝐶ሶ Liquid 𝑄෠ 𝐵 𝐻෠ 3 − 𝐻෠2
0 Ideal Mixtures 𝐶. 𝑂. 𝑃 = =
𝑊෡𝑠 𝐻෠ 4 − 𝐻෠3
𝑈= 𝑈𝐼 + 𝑈 𝐼𝐼 = constant
𝜙 = 𝑓Τ𝑃 = fugacity coefficient Hydrocarbons make ideal mixtures
𝑃𝐼 = 𝑃𝐼𝐼 𝑇 𝐼 = 𝑇 𝐼𝐼 Path 𝑷 ෡
𝑺 ෡
𝑯 Energy Flow Path 𝑻 𝑷 ෡
𝑺 ෡
𝑯 Energy Flow
𝑃 𝑉
ഫ Volume and Enthalpy 𝛥𝑚𝑖𝑥 𝑉 𝐼𝑀 = 0 .

1 𝑅𝑇 1 𝑅𝑇 changes upon mixing 1−2 𝑃1 , 𝑃2 𝑆መ1 = 𝑆መ2 ෡1, 𝐻

𝐻 ෡𝑃 = 𝑉෠1 𝑃2 − 𝑃1
෡2 𝑊 1−2 𝑇1 , 𝑇2 𝑃1 , 𝑃2 𝑆መ1 , 𝑆መ2 ෡1 = 𝐻
𝐻 ෡2 --
ഫ𝐼 = 𝐺
𝐺 ഫ 𝐼𝐼 ln𝜙 = න 𝑉
ഫ− 𝑑𝑃 = න − 𝑃 𝑑ഫ
𝑉 − ln𝑍 + 𝑍 − 1 𝛥𝑚𝑖𝑥 𝐻𝐼𝑀 = 0
𝑅𝑇 𝑃 𝑅𝑇 𝑉
ഫ are equal to zero
𝐺
ഫ must be minimum 0 𝑉
ഫ= ∞ 2 − 3 𝑃2 = 𝑃3 𝑆መ2 , 𝑆መ3 ෡2 , 𝐻
𝐻 ෡3 𝑄෠𝐵 = 𝐻෡3 − 𝐻
෡2 2 − 3 𝑇2 = 𝑇3 𝑃2 = 𝑃3 𝑆መ2 , 𝑆መ3 ෡2 , 𝐻
𝐻 ෡3 𝑄෠𝐵 = 𝐻
෡3 − 𝐻
෡2
𝐺ҧ𝑖𝐼𝑀 = 𝐺
ഫ𝑖 + 𝑅𝑇ln𝑥𝑖 𝑓𝑖ҧ𝐼𝑀 = 𝑥𝑖 𝑓𝑖 3−4 𝑃3 , 𝑃4 𝑆መ3 = 𝑆መ4 ෡3 , 𝐻
𝐻 ෡4 ෡𝑇 = 𝐻
𝑊 ෡4 − 𝐻
෡3 3−4 𝑇3 , 𝑇4 𝑃3 , 𝑃4 𝑆መ3 = 𝑆መ4 ෡3 , 𝐻
𝐻 ෡4 ෡𝑠 = 𝐻
𝑊 ෡4 − 𝐻
෡3
Stability Criteria van der ln𝜙 = 𝑍 − 1 − ln 𝑍 − 𝐵 − 𝐴Τ𝑍
Waals EOS 4 − 1 𝑃4 = 𝑃1 𝑆መ4 , 𝑆መ1 ෡4, 𝐻
𝐻 ෡1 𝑄෠𝐶 = 𝐻
෡1 − 𝐻
෡4 4−1 𝑇4 , 𝑇1 𝑃4 = 𝑃1 𝑆መ4 , 𝑆መ1 ෡4, 𝐻
𝐻 ෡1 𝑄෠𝐶 = 𝐻
෡1 − 𝐻
෡4
𝜕𝑃 Equation of State Mixing Rules
𝐶𝑉 > 0 and <0
𝜕ഫ
𝑉 𝑇 Fugacity coefficient: Peng-Robinson EOS
𝐶
𝐶
Low Pressure Approximations
must be satisfied in each phase Clausius-Clapyeron Equation Fugacity Dalton’s Law Raoult’s Law
𝐴 𝑍+ 1+ 2 𝐵 𝑎𝑚𝑖𝑥 = ා ෍ 𝑦𝑖 𝑦𝑗 𝑎𝑖𝑗
ln𝜙 = 𝑍 − 1 − ln 𝑍 − 𝐵 − ln
Gibbs Phase Rule 2𝐵 2 𝑍+ 1− 2 𝐵 𝑗=1
𝑃 𝑣𝑎𝑝 𝐻 𝑣𝑎𝑝 1
𝛥ഫ 1 𝑓 𝐿 = 𝑃 𝑣𝑎𝑝 𝑃𝑖 = 𝑦𝑖 𝑃 Valid if low P
𝑥𝑖 𝑃𝑖𝑣𝑎𝑝 = 𝑦𝑖 𝑃
𝑖=1
ln 2𝑣𝑎𝑝 = − − ideal mixture
𝐷𝐹 = 𝐶 − 𝑃𝐻 + 2 𝑃1 𝑅 𝑇2 𝑇1 𝐿 𝑉
𝑃𝑣𝑎𝑝 Work Flow 𝑏𝑚𝑖𝑥 = ෍ 𝑦𝑖 𝑏𝑖 𝑎𝑖𝑗 = 𝑎𝑖𝑖 𝑎𝑗𝑗 1 − 𝑘𝑖𝑗 𝑓 =𝑓 𝑃𝑖 = partial pressure 𝑥𝑖 = liquid mole fraction 𝑦𝑖 = vapor mole fraction
𝐷𝐹 = degrees of freedom ഫ 𝑣𝑎𝑝 = 𝐿𝑣
𝛥𝐻
- Follow steps from volumetric EOS section to calculate 𝑍𝑉 and 𝑍𝐿
𝐶 = number of components 𝑘𝑖𝑗 = binary interaction parameter
For a solid
Valid if ideal mixture 𝑃𝑖𝑣𝑎𝑝 𝑃 − 𝑃2𝑣𝑎𝑝
𝑉 𝐿
- Compute 𝑓 and 𝑓 by inputting 𝑍𝑉 and 𝑍𝐿 into above equations 𝐻 𝑣𝑎𝑝
𝛥ഫ = enthalpy of vaporization 𝐾𝑖 = 𝑥1 =
𝑃𝐻 = number of phases - Iterate 𝑃 until 𝑓 𝑉 = 𝑓 𝐿 𝑘𝑖𝑗 = 0 for HC-HC pairs 𝑓 𝑆 = 𝑃 𝑠𝑎𝑡 of ideal gases 𝑃 𝑃1𝑣𝑎𝑝 − 𝑃2𝑣𝑎𝑝
𝑇 = absolute temperature = 𝐾

Created by James Riddle with guidance from Dr. Matthew T. Balhoff Contact balhoff@mail.utexas.edu with comments/suggestions
 Properties of Reservoir Fluids
Conversions and Constants Phase Behavior
1 kPa = 0.1450 psi 1 in = 2.54 cm 1 acre = 43560 ft2 1 m3 = 6.2898 bbl R = 459.67 + °F 1 lbm = 453.59 g Clausius-Clapeyron Binary Mixtures Real Mixtures
1 MPa = 10 bar 1 ft = 0.3048 m 1 m2 = 10.764 ft2 1 bbl = 5.6146 ft3 K = 273.15 + °C
1 cp = 1 mPa-s 𝜕𝑃𝑣𝑎𝑝 𝐿𝑣 𝑦𝑖 = 𝐾𝑖 𝑥𝑖 𝑧𝑖 = 𝑥𝑖 𝑛ത 𝐿 + 𝑦𝑖 𝑛ത𝑣
𝑖𝑓 ෍ 𝑧𝑖 𝐾𝑖 > 1 𝑃 < 𝑃𝐵𝑃
1 atm = 14.696 psi 1 mile = 5280 ft 1 bbl = 42 US gal °F = 1.8 °C + 32 = If summation is equal to
𝜕𝑇 𝑇 𝑉𝑀𝑔 − 𝑉𝑀𝐿 1 − 𝐾2 𝑧𝑖 − 𝑥𝑖 1, pressure is at the
1 atm = 1.013 bar 1 mile = 1,609 m 1 ft3 = 7.4805 gal 1 BTU = 1.055 kJ 𝑥1 = 𝑛ത𝑣 = 𝑧 bubble point or dew point
𝐿𝑣 = heat of vaporization 𝐾1 − 𝐾2 𝑦𝑖 − 𝑥𝑖 𝑖𝑓 ෍ 𝑖ൗ𝐾 > 1 𝑃> 𝑃𝐷𝑃
Molar Mass of Air = 28.966 g/mol Gas Constant = 10.732 psia ⋅ ft 3Τlbmol ⋅ R Water density at SC = 62.37 lbm Τft 3 𝑖
𝑉𝑀𝑔 = molar volume of gas 𝐾 = K factor or equilibrium ratio
Standard Pressure = 14.696 psia Gas Constant = 1.9859 BTUΤlbmol ⋅ R Molar Volume of ideal gas = RT SCΤPSC
𝑉𝑀𝐿 = molar volume of liquid 𝑧𝑖 = overall mole fraction of component 𝑖 Flash Calculation
IG IG
Standard Temperature = 60°F VM = 22.4 LΤgmol @ 1.013 bar VM = 379.3 scfΤlbmol @ 14.696 psia 𝑧𝑖 Iterate 𝑛ത 𝐿 until both
Assume 𝐿𝑣 is constant, 𝑥𝑖 = 𝑦𝑖 = 𝐾𝑖 𝑥𝑖
Reservoir Fluid Components 𝑉𝑀𝐿 is negligible, and liquid 𝑛ത𝐿 + 𝐾𝑖 1 − 𝑛ത𝐿 σ 𝑦𝑖 = 1 & σ 𝑥𝑖 = 1

Pressure (psia)
Ideal Gas Law vapor Tie-line
Composition of Reservoir Fluid 𝑙𝑖𝑞𝑢𝑖𝑑 𝑚𝑜𝑙𝑒𝑠 𝑣𝑎𝑝𝑜𝑟 𝑚𝑜𝑙𝑒𝑠
Major Components of Reservoir Fluids 0.1 𝑣𝑎𝑝 𝑧1 𝑛ത𝐿 + 𝑛ത𝑣 = 1 𝑛ത 𝐿 = 𝑛ത 𝑣 =
𝑃2 𝐿𝑣 1 1 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠

Overall Mole Fraction, 𝑧𝑖

𝑥1 𝑦1
Hydrocarbons Propane n-Butane In general, as carbon ln 𝑣𝑎𝑝 = −
𝑃1 𝑅 𝑇1 𝑇2 Ternary Diagrams
0.01 number increases
1. Paraffins
mole fraction decreases Pure Substance Component 3
- Saturated: Carbons have as many Hydrogens as possible 1000
iso-Butane n-Pentane 10−3 0 20 40 60 80 100
Diagram for a Each corner

Vapor Pressure (psia)

𝐶𝑛 𝐻2𝑛+2 Composition, mol % component 1
Slope of line single pressure 80 represents
- As carbon # increases, 𝑇 𝑐 increases and 𝑃 𝑐slightly decreases 10−4 depends on 100 & temperature 100% of that
- Waxes form when carbon # above 𝐶20 fluid type liquid component and
*Pedersen et al 60

Temperature 𝑅
- Specific gravity ≈ 0.65 (1983, 1984) vapor each leg signifies
Most Common Cycloalkanes 10−5
0 10 20 30 40 10 a binary mixture
Cyclopentane Cyclohexane 𝑧1 40
2. Naphthenes/Cycloalkanes (𝐶5 − 𝐶100) Carbon Number 𝑃𝑣𝑎𝑝
linear on
*Pattern observed in compositions of gas condensate and oil semi-log plot 𝑥1 𝑦1
- Specific gravity ≈ 0.88 − 0.9
reservoir fluids. For 𝐶𝑛 ≥ 𝐶6 , linear relationship on semi-log scale 1 20
Temperature−1 1Τ𝑅 Vapor Liquid
2-phase
3. Aromatics (𝐶6 − 𝐶20) Benzene Building block
Mass and Mole Fraction Conversions Assumptions above not always 0 20 40 60 80 100
- Excellent solvents for dissolving Resins & Asphaltenes 𝑤𝑖 valid. Cox Chart more accurate. Composition, mol % component 1 Component 1 Component 2
of Aromatics is 𝑧𝑖 𝑀𝑊𝑖
- Specific gravity ≈ 0.88 − 0.9 𝑤𝑖 = 𝑧𝑖 =
usually Benzene 𝑀𝑊𝑇 𝑀𝑊𝑖 𝑛𝑇 Classification of Reservoir Fluids
Resins & Asphaltenes 𝑤𝑖
𝑀𝑊𝑇 = ෍ 𝑧𝑖 𝑀𝑊𝑖 𝑛𝑇 = ෍ ൗ𝑀𝑊 Laboratory and Field Characteristics
𝑖
- Complex, large molecules containing mainly C & H with S, O, or N
𝑤𝑖 = mass fraction of component 𝑖 𝑛 𝑇 = total moles
Initial GOR Oil Gravity Initial 𝐵𝑜 𝐶7+ Fraction
- Resins dissolve in petroleum but Asphaltenes do not dissolve (need aromatics) Fluid Type 𝑇 𝑅𝐶 Phase Behavior
- Resins and Asphaltenes increase the fluid’s viscosity and determine its color
scf/STB °API RB/STB Mole %
𝑀𝑊𝑇 = total molecular weight

Reservoir Fluid Properties Dry Gas > 𝑇 𝑐𝑟𝑐 -- -- -- -- Single phase at all pressures and temperatures

Gas phase in reservoir at all P & T.

Reservoir Conditions Surface 𝐵𝑔 (1 − 𝑅𝑣𝑖 𝑅𝑠 ) + 𝐵𝑜 (𝑅𝑣𝑖 − 𝑅𝑣 ൯ 𝐵𝑔 Calculation Wet Gas > 𝑇 𝑐𝑟𝑐 > 50,000 -- -- -- Separator within two-phase region.
𝐵𝑡𝑔 =
Isothermal Conditions 1 − 𝑅𝑠 𝑅𝑣
𝑃 𝑆𝐶 𝑧𝑇 𝑟𝑐𝑓 Gas All gas initially; As pressure falls below
P > BP P < BP 𝐵𝑔 = [=] Condensate 𝑇 𝑐 − 𝑇 𝑐𝑟𝑐 3300 − 50000 40 − 60 -- < 12.5 dew point a liquid phase forms
Gas
1 1.2 1 + 2 𝑅𝐵 𝑇 𝑆𝐶 𝑃 𝑠𝑐𝑓
Gas 𝐵𝑔 = 𝑅𝑣 = 𝑇 𝑅𝐶 close to 𝑇 𝑐 . Key difference between volatile and black
OIL 1 1.1
𝐵𝑡𝑔 = [=]
𝑠𝑐𝑓 𝑃 = 𝑝𝑠𝑖𝑎 𝑇 = 𝑅 Volatile Oil < 𝑇𝑐 2000 − 3300 42 − 55 1.7 − 3.0 12.5 − 20 oils is that the gas phase can produce liquid at surface.
Oil
2 + 2.1 As reservoir pressure falls below
1.1 1.1 1.1 Specific Gravity Black Oil < 𝑇𝑐 200 − 2000 15 − 45 1.1 − 1.7 25 − 50 bubble point, gas phase forms.
Oil 𝜌𝑜 Undersaturated Oil phase in reservoir at all P & T.
1.2
Piston

𝛾𝑜 = Oil < 𝑇𝑐 200 − 2000 15 − 45 1.1 − 1.7 25 − 50 Separator within two-phase region.
𝜌𝑤 𝑆𝐶

𝐵𝑜 (1 − 𝑅𝑠𝑖 𝑅𝑣 ) + 𝐵𝑔 (𝑅𝑠𝑖 − 𝑅𝑠 ൯ 𝑀𝑊𝑔 Dead Oil < 𝑇𝑐 -- 5 − 15 1.0 − 1.1 > 50 Single phase at all pressures and temperatures.
𝐵𝑡𝑜 = 𝛾𝑔 =
1 − 𝑅𝑠 𝑅𝑣 𝑀𝑊𝑎𝑖𝑟 𝑇 𝑐𝑟𝑐 = cricondentherm
Legend Gas Specific Gravity
2.1 2 2.1 𝑀𝑊 = molecular weight API Classification
1.1 – Free Gas
1.2 – Volatilized Oil
1 + 2 𝑅𝐵
1.0 0.934 0.876 0.825 0.78

𝐵𝑜 = 𝑅𝑠 = 𝐵𝑡𝑜 = [=] API Gravity

Fluid Type °API Gravity Dead Oil Light Crude Oil
2.1 – Solution Gas Oil
2.2 2.2 2.2 1.2 + 2.2 𝑆𝑇𝐵 Light Crude Oil > 31.1 Black Oil
2.2 – Free Oil 141.5
1 – Gaseous Phase (Gas + Volatilized Oil) 𝑟𝑐𝑓 𝛾𝑜 = Medium Oil 22.3 − 31.1 Medium Oil
2 – Oleic Phase (Oil + Solution Gas) 𝐵𝑜 [=] 𝑅𝐵ൗ𝑆𝑇𝐵 𝑅𝑠 [=] 𝑠𝑐𝑓ൗ 𝐵𝑔 [=] ൗ𝑠𝑐𝑓 𝑅𝑣 [=] 𝑆𝑇𝐵ൗ𝑠𝑐𝑓 °𝐴𝑃𝐼 + 131.5 Volatile Oil
𝑆𝑇𝐵 Heavy Crude Oil 10.0 − 22.3 Heavy Crude Oil

Fluid Properties – Pressure Dependence Compressibility Extra Heavy Oil < 10.0 Extra Heavy Gas Condensate
0.04 10 20 30 40 50
z-Factor 1 𝜕𝑉 °API Gravity
𝑐=− [=]𝑝𝑠𝑖 −1
𝑉 𝜕𝑃
0.03 1.5 60
𝑇 Undersaturated Oil Black Oil Volatile Oil
1 1 𝜕𝑧
𝐁𝐭𝐨 𝑐𝑔 = − Initial Pressure Reservoir
0.02 𝑩𝒈 0.02 1.2 1 40 𝑃 𝑧 𝜕𝑃 𝑇 Isothermal
𝐁𝐨
1 𝜕𝐵𝑜 𝜕𝑅𝑠
0.01 𝝁𝒈 20 𝑐𝑜 = − − 𝐵𝑔
BP 𝐵𝑜 𝜕𝑃 𝜕𝑃 Surface
𝑇 𝑇
0.01 1.1 Conditions
400 800 1200 1600 400 800 1200 1600 𝑐𝑡 = 𝑐𝑜 𝑆𝑜 + 𝑐𝑔 𝑆𝑔 + 𝑐𝑤 𝑆𝑤 + 𝑐𝑅
Pressure (psi) Pressure (psi)

Z-Factor Approximation Properties of Brine

Law of Corresponding States Ion Composition Compressibility Gas Condensate Wet Gas Dry Gas
- Cations: positive ions in solution 𝜕 1 1 𝜕𝑃 1 𝜕𝜌𝑤
𝑃𝑐𝑝 = ෍ 𝑦𝑖 𝑃𝑐,𝑖 𝑇𝑐𝑝 = ෍ 𝑦𝑖 𝑇𝑐,𝑖 - most common: 𝑁𝑎+ , 𝐶𝑎2+ , 𝑀𝑔2+, 𝐹𝑒 2+ 𝑐𝑤 = 𝐵𝑤 =− =
𝜕𝑃 𝐵𝑤 𝐵𝑤 𝜕𝐵𝑤 𝑇 𝜌𝑤 𝜕𝑃 𝑇
𝑃𝑐𝑝 = pseudocritical pressure - Anions: negative ions in solution
Quality Lines or
- most common: 𝐶𝑙− , 𝑆𝑂42−, 𝐻𝐶𝑂3−, 𝐶𝑂32− iso-vols
𝑇𝑐𝑝 = pseudocritical temperature Mixing Brines
Dissolved Solids - Certain mixtures of brines can cause solids to drop out
Represent constant
𝑃𝑝𝑟 = 𝑃ൗ𝑃 𝑇𝑝𝑟 = 𝑇ൗ𝑇 liquid volume
𝑝𝑐 𝑝𝑐 Parts Per Million (PPM) of solution called scale
𝑃𝑝𝑟 = pseudoreduced pressure 𝑔𝑟𝑎𝑚𝑠 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑑 𝑠𝑜𝑙𝑖𝑑𝑠 if actual 𝐾𝑠𝑝 ≥ theoretical 𝐾𝑠𝑝
𝑃𝑃𝑀[=]
𝑇𝑝𝑟 = pseudoreduced temperature 106 𝑔𝑟𝑎𝑚𝑠 𝑜𝑓 𝑏𝑟𝑖𝑛𝑒 scale is likely to form
*Once 𝑃𝑝𝑟 and 𝑇𝑝𝑟 are known, can use a chart 𝑇𝐷𝑆 𝑚𝑔Τ𝐿 𝐾𝑠𝑝,𝑎 = 𝐴 𝐶
Laboratory Measurements
or correlation to determine the z-factor [=]𝑃𝑃𝑀 𝑇𝐷𝑆 = total 𝐾𝑠𝑝,𝑡 = exp −𝛥𝐺 Τ𝑅𝑇
𝛾𝑤 dissolved solids Flash Vaporization Test Differential Vaporization Test
𝐴 = anion molarity 𝛥𝐺[=] 𝑐𝑎𝑙Τ𝑚𝑜𝑙 𝑇[=]𝐾
Hall-Yarborough Correlation (1973) Miliequivalents Per Liter 𝐴 [=] 𝑚𝑜𝑙/𝐿 𝑃𝐵𝑃 Vented Vented
−1 𝑅 = 1.986[=] 𝑐𝑎𝑙Τ𝑚𝑜𝑙 𝐾
Gas Gas
𝑡 = 𝑇𝑝𝑟 𝑖𝑜𝑛 𝑚𝑔Τ𝐿 𝑖𝑜𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑚𝑒𝑞 𝐶 = cation molarity
2
[=] 𝛥𝐺 = ෍ 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ෍ 𝑟𝑒𝑎𝑐tan𝑡𝑠 𝑃𝐵𝑃
𝐴 = 0.06125𝑡 exp −1.2 1 − 𝑡 𝑀𝑊𝑖𝑜𝑛 𝐿 𝑉𝑇 Liquid Gas
𝑉𝐵 Liquid Gas
𝐵 = 14.76𝑡 − 9.76𝑡 2 + 4.58𝑡 3 𝑉𝑇
Stiff Diagram Formation Water Analysis Liquid Liquid
Liquid Gas Liquid Gas
𝐶 = 90.7𝑡 − 242.2𝑡 2 + 42.4𝑡 3 Ion Concentration 𝑚𝑒𝑞Τ𝐿
1000 0 1000 Hg Hg Liquid
𝐷 = 2.18 + 2.82𝑡 Na Cl Liquid Liquid
Hg Hg
Hg Hg Hg
𝑥 + 𝑥2 + 𝑥3 − 𝑥4 Ca HCO3
𝑓(𝑥) = − 𝐴𝑥 − 𝐵𝑥 2 + 𝐶𝑥 𝐷 100 100 First Step Second Step Third Step Fourth Step Hg Hg
1−𝑥 3
Mg SO4 aka Constant Mass Expansion - Good for calculating bubble point
set 𝑓(𝑥) = 0 and solve for x 100 100 First Step Second Step
𝐴𝑃𝑝𝑟 Fe CO3 Standard pressure can be achieved because of the gas venting
𝑧= 𝑉𝑇 𝑇𝑜𝑡𝑎𝑙 𝑉𝑜𝑙. 𝑉𝑇
𝑥 100 100 Comparing diagram shapes can confirm = < 1 when 𝑃 > 𝑃𝐵𝑃
Other correlations include Dranchuk If mix brines, the resulting stiff diagram will be a reservoir communication, contamination of 𝑉𝐵 𝑉𝑜𝑙. 𝑎𝑡 𝑃𝐵𝑃 𝑉𝐵 𝐿𝑖𝑞𝑢𝑖𝑑 𝑉𝑜𝑙. 𝑖𝑛 𝑐𝑒𝑙𝑙 𝑅𝐵 𝐺𝑎𝑠 𝑟𝑒𝑚𝑜𝑣𝑒𝑑 𝑖𝑛 𝑠𝑐𝑓 𝑠𝑐𝑓
𝐹 𝐹 𝐵𝑜𝐷 = [=] 𝑅𝑠𝐷 = [=]
Abou-Kassem (1975) & Standing and Katz (1942) weighted average of the individual stiff diagrams fresh water, or incursion of foreign water 𝑉𝑜𝑙. 𝑎𝑡 𝑠𝑡𝑑. 𝑃&𝑇 𝑏𝑏𝑙 𝑂𝑖𝑙 𝑉𝑜𝑙. 𝑎𝑡 𝑠𝑡𝑑. 𝑃&𝑇 𝑏𝑏𝑙

Developed Miscibility Separator Test

Separator Test Results
Evolution of Developed Miscibility
Linear Scale

- Best estimate of 𝐵𝑜 and 𝑅𝑠 at bubble point

𝐶4 𝐶4 𝐶4 Optimal °𝐴𝑃𝐼
- Multiple test results yield optimal separator pressure
Pressure 𝑅𝑠𝑆𝑏
80 Injected gas and 80 Gas composition 80 𝑂𝑖𝑙 𝑉𝑜𝑙. 𝑖𝑛 𝑐𝑒𝑙𝑙 𝑅𝐵 𝐵𝑜𝑆𝑏
oil immiscible moves toward 𝐵𝑜𝑆𝑏 = [=]
𝑂𝑖𝑙 𝑉𝑜𝑙. 𝑖𝑛 𝑠𝑡𝑜𝑐𝑘 tan𝑘 𝑆𝑇𝐵
60 initially 60 Plait Point 60 50 100 150 200 250 300
Dilution Developed 𝐺𝑎𝑠 𝑉𝑜𝑙. 𝑖𝑛 𝑠𝑒𝑝𝑎𝑟𝑎𝑡𝑜𝑟 + 𝑠𝑡𝑜𝑐𝑘 𝑡𝑎𝑛𝑘 𝑠𝑐𝑓 Separator Pressure (psig)
line Tie-lines Miscibility
40
𝑅𝑠𝑆𝑏 = [=] - Optimal pressure occurs when 𝑅𝑠𝑆𝑏 and 𝐵𝑜𝑆𝑏 are minimized and °𝐴𝑃𝐼 is at a maximum
40 40 𝑂𝑖𝑙 𝑉𝑜𝑙. 𝑖𝑛 𝑠𝑡𝑜𝑐𝑘 𝑡𝑎𝑛𝑘 𝑆𝑇𝐵
2-phase region - Most black oils have optimal separator pressures of 100-120 psig at normal temperatures
Initial Oil
20 𝑦𝑖 20 20 Correcting Lab Measurements
Injected 𝑧𝑖 𝑥𝑖
Gas Pressure Greater than Bubble Point Pressure Equals BP Pressure Less than Bubble Point
𝐶𝑂2 𝐶10 𝐶𝑂2 𝐶10 𝐶𝑂2 𝐶10 𝑉𝑇 𝐵𝑜𝑆𝑏 𝐵𝑜𝑆𝑏
𝐵𝑜 = 𝐵𝑜𝑆𝑏 𝑅𝑠 = 𝑅𝑠𝑆𝑏 𝐵𝑜 = 𝐵𝑜𝑆𝑏 𝑅𝑠 = 𝑅𝑠𝑆𝑏 𝐵𝑜 = 𝐵𝑜𝐷 𝑅𝑠 = 𝑅𝑠𝑆𝑏 − 𝑅𝑠𝐷𝑏 − 𝑅𝑠𝐷
- Developed miscibility (miscible displacement) can be achieved if the initial oil or injected gas composition is above the critical tie-line 𝑉𝐵 𝐹
𝐵𝑜𝐷𝑏 𝐵𝑜𝐷𝑏

Created by James Riddle with guidance from Dr. Matthew T. Balhoff Contact balhoff@mail.utexas.edu with comments/suggestions