Chapter 4: Fundamentals of Material Balances

Non-Reactive Systems
General Balance Equation: 𝑖𝑛𝑝𝑢𝑡 + 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑜𝑢𝑡𝑝𝑢𝑡 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
In steady-state systems, accumulation = 0, 𝑖𝑛𝑝𝑢𝑡 + 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑜𝑢𝑡𝑝𝑢𝑡 − 𝑐𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = 0
In non-reactive, steady-state systems, generation, consumption = 0, 𝑖𝑛𝑝𝑢𝑡 − 𝑜𝑢𝑡𝑝𝑢𝑡 = 0 (accumulation
likely 0)
Degrees of freedom in a non-reactive system: 𝐷𝑂𝐹 = #𝑢𝑛𝑘𝑛𝑜𝑤𝑛𝑠 − #𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑚𝑎𝑠𝑠 𝑏𝑎𝑙𝑎𝑛𝑐𝑒𝑠 −
#𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐𝑎𝑡𝑖𝑜𝑛𝑠 − #𝑝ℎ𝑦𝑠𝑖𝑐𝑎𝑙 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑖𝑒𝑠/𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠

Reactive Systems:
(𝑛𝐴 )𝑓𝑒𝑒𝑑 −(𝑛𝐴 )𝑠𝑡𝑜𝑖𝑐ℎ
Fractional Excess: 𝑓. 𝑒. (𝐴) = (𝑛𝐴 )𝑠𝑡𝑜𝑖𝑐ℎ
Percentage Excess: %𝑒 = 𝑓. 𝑒. (100%)

𝑚𝑜𝑙𝑒𝑠 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
Fractional Conversion: 𝑓 = Percentage Conversion : %𝑐 = 𝑓(100%)
𝑚𝑜𝑙𝑒𝑠 𝑓𝑒𝑑

Extent of reaction method: 𝑛 = 𝑛0 + ∑ 𝜈𝑖𝑗 𝜉𝑖 for each reactive species

Degrees of freedom: 𝐷𝑂𝐹 = #𝑢𝑛𝑘𝑛𝑜𝑤𝑛𝑠 + #𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 −

#𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑣𝑒 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 − #𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑛𝑜𝑛𝑟𝑒𝑎𝑐𝑡𝑖𝑣𝑒 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 − #𝑠𝑝𝑒𝑐𝑠/𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠
Atomic species method: follows general balance equation, convert to amount of mol (ex C, H, O, etc.)
Degrees of freedom: 𝐷𝑂𝐹 = #𝑢𝑛𝑘𝑛𝑜𝑤𝑛𝑠 − #𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑎𝑡𝑜𝑚𝑖𝑐 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 −
#𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑏𝑎𝑙𝑎𝑛𝑐𝑒𝑠 𝑜𝑛 𝑛𝑜𝑛𝑟𝑒𝑎𝑐𝑡𝑖𝑣𝑒 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 − #𝑠𝑝𝑒𝑐𝑠/𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠
Molecular species method: follows general balance equation, use molecules instead of atomic species
Degrees of freedom: 𝐷𝑂𝐹 = #𝑢𝑛𝑘𝑛𝑜𝑤𝑛𝑠 + #𝑖𝑛𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠 − #𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 −
#𝑠𝑝𝑒𝑐𝑠/𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛𝑠
𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑓 𝑚𝑜𝑙 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑠 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠)
Equilibrium constant: 𝐾(𝑇) = 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑜𝑓 𝑚𝑜𝑙 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑠 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

𝑚𝑜𝑙 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

Yield: 𝑦𝑖𝑒𝑙𝑑 = 𝑚𝑜𝑙 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑖𝑓 𝑛𝑜 𝑠𝑖𝑑𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛𝑠,𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 𝑓𝑢𝑙𝑙𝑦 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

𝑚𝑜𝑙 𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

Selectivity: 𝑠𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 =
𝑚𝑜𝑙 𝑢𝑛𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑝𝑟𝑜𝑑𝑢𝑐𝑡

Theoretical oxygen: mol or n of O2 required for complete combustion

Theoretical air: amount of air containing theoretical oxygen
(𝑛𝐴 )𝑓𝑒𝑒𝑑 −(𝑛𝐴 )𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
Excess air: 𝑒. 𝑎. = (𝑛𝐴)𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙
, multiply by 100 for %. In calculation, 50% excess is written as
1.5 (100% required + 50% excess)
Chapter 5: Single-Phase Systems
Liquid and solid density equations:
1 𝑥𝑖
Volume Additivity: ̅ = ∑𝑛𝑖=1
𝜌 𝜌𝑖

Average of Pure-component Densities: 𝜌̅ = ∑𝑛𝑖=1 𝑥𝑖 𝜌𝑖

̅
𝑃𝑀
Density: 𝜌 =
𝑅𝑇

Ideal Gases
Ideal Gas Law: 𝑃𝑉 = 𝑛𝑅𝑇 𝑜𝑟 𝑃𝑉̇ = 𝑛̇ 𝑅𝑇 𝑜𝑟 𝑃𝑉̂ = 𝑅𝑇
𝑉
Specific Molar Volume: 𝑉̂ =
𝑛
𝑉
Specific Volume: 𝑉̂ =
𝑚
𝑃𝑉 𝑇
Converting to STP: ̂𝑠
= 𝑛 , Ps = 1 atm, Vs = 0.022415 m^3, Ts = 273 K
𝑃𝑠 𝑉 𝑇𝑠

Dalton’s Law: 𝑝𝐴 = 𝑦𝐴 𝑃, ∑ 𝑝𝑖 = 𝑃
Amagat’s Law: 𝑣𝐴 = 𝑦𝐴 𝑃, ∑ 𝑣𝑖 = 𝑉
Equations of State
Virial, Van der Waals, SRK (section 5.3)
Compressibility Factor
𝑃𝑉 = 𝑧𝑛𝑅𝑇
Critical Conditions
̂
𝑃𝑐 𝑉 𝑃 𝑇
𝑉𝑟 𝑖𝑑𝑒𝑎𝑙 = 𝑃𝑟 = 𝑇𝑟 =
𝑅𝑇𝑐 𝑃𝑐 𝑇𝑐

Newton’s Corrections for Hydrogen and Helium

Temperature: 𝑇𝑐 𝑎 = 𝑇𝑐 + 8 𝐾
Pressure: 𝑃𝑐 𝑎 = 𝑃𝑐 + 8 𝑎𝑡𝑚
Kay’s rule: 𝑇𝑐′ = ∑ 𝑦𝑖 𝑇𝑐(𝑖) and 𝑃𝑐′ = ∑ 𝑦𝑖 𝑃𝑐(𝑖) for mixtures of gases, condensable
components only
Chapter 6: Multiphase Systems
𝑑𝑝∗ ∆𝐻̂𝑉 𝑑(ln 𝑝∗ ) ̂𝑉
∆𝐻
Clapeyron Equation: = ̂𝑔 −𝑉
̂𝑙 )
 1 =−
𝑑𝑡 𝑇(𝑉 𝑑( ) 𝑅
𝑇

̂𝑉
∆𝐻
Clausius-Clapeyron Equation: ln 𝑝∗ = − + 𝐵, B depends on substance
𝑅𝑇
𝐵
Antoine Equation: 𝑙𝑜𝑔10 𝑝∗ = 𝐴 − , returns p* in mm Hg using T in degrees C.
𝑇+𝐶

Gibbs Phase Rule

Degrees of Freedom: 𝐷𝑂𝐹 = 2 + 𝑐 − 𝜋 − 𝑟, DOF is the number of intensive
variables required to describe the state of the system.
𝑝𝐻2 𝑂
Relative Humidity: ℎ𝑟 =
𝑝∗ 𝐻 𝑂 (𝑇)
2

𝑚𝐻2 𝑂,𝑣
Absolute Humidity: ℎ𝑎 =
𝑚𝑑𝑟𝑦 𝑎𝑖𝑟

Raoult’s Law
For one condensable component: 𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑝∗ 𝑖 (𝑇)
For multiple condensable components: 𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝑝∗ 𝐴 (𝑇)
Use for concentrated solutions or solutions of structurally similar compounds.
Henry’s Law
For multiple condensable components: 𝑝𝐴 = 𝑦𝐴 𝑃 = 𝑥𝐴 𝐻∗ 𝐴 (𝑇)
Use for dilute solutions!
Calculation of Bubble Point Temperature and Pressure
Temperature: 𝑃 = 𝑃 ∑𝑚 𝑚 ∗
𝑖=1 𝑦𝑖 = ∑𝑖=1 𝑥𝑖 𝑝 𝑖 (𝑇𝑏𝑝 )

Solve by: Substituting pi*(Tbp) for its equivalent Antoine Equation, use Excel
Goal-Seek/Solver
Pressure: 𝑃𝑏𝑝 = 𝑃𝑏𝑝 ∑𝑚 𝑚 ∗
𝑖=1 𝑦𝑖 = ∑𝑖=1 𝑥𝑖 𝑝 𝑖 (𝑇)

Solve by : Direct Calculation

Calculation of Dew Point Temperature and Pressure
𝑦𝑖
Temperature : 𝑃 ∑𝑘𝑖=1 =1
𝑝∗ 𝑖 (𝑇𝑑𝑝 )

Solve by: Substituting pi*(Tdp) for its equivalent Antoine Equation, use Excel
Goal-Seek/Solver
1
Pressure: 𝑃𝑑𝑝 = 𝑦
∑𝑘 𝑖
𝑖=1𝑝∗ (𝑇)
𝑖

Solve by: Direct calculation

Chapter 7: Energy and Energy Balances

𝑚𝑢2
Kinetic energy: 𝐸𝑘 =
2

Potential energy: 𝐸𝑝 = 𝑚𝑔𝑧

̂=𝑈
Specific enthalpy: 𝐻 ̂ + 𝑃𝑉̂

General Energy Balance: ∆𝑈 + ∆𝐸𝑘 + ∆𝐸𝑝 = 𝑄 − 𝑊

Potential simplifications for a closed system:
1. If no reactions, isothermal, small changes in pressure (a few atm), then
∆𝑈 ≈ 0
2. If no system acceleration, then ∆𝐸𝑘 = 0
3. If no change in elevation, then ∆𝐸𝑝 = 0
4. If system and surroundings have the same T, or the system is well insulated,
Q=0
5. If there is no resisting force on the system boundary, electric current, or
radiation across the system boundary, W=0
For an Open system with n inputs and k outputs, absorbing heat at the rate 𝑄̇ and
̇ at steady state:
performing shaft work at a rate of 𝑊𝑠
𝑘 𝑛
𝑢𝑗 2 𝑢𝑖 2
̂𝑗 +
∑ 𝑚̇𝑗 (𝐻 ̂𝑖 +
+ 𝑔𝑧𝑗 ) − ∑ 𝑚̇𝑖 (𝐻 + 𝑔𝑧𝑖 ) = 𝑄̇ − 𝑊̇𝑠
2 2
𝑗=1 𝑖=1

̇ ̂ (𝐻𝑜𝑢𝑡 − 𝐻𝑖𝑛) we can simplify to: ∆𝐻̇ + ∆𝐸̇ + ∆𝐸̇ = 𝑄̇ − 𝑊̇

Since ∆𝐻̇ = 𝑚∆𝐻 𝑘 𝑝 𝑠

In general: potential/kinetic energies will be negligible

 ∆𝐻̇ = 𝑄̇ − 𝑊̇𝑠
If no shaft work is performed: ∆𝐻̇ = 𝑄̇
For a steam turbine: 𝑊̇𝑠 = −∆𝐻̇
For a fluid flow process: use the Bernoulli equation when possible

𝑃 𝑢2 𝑄̇ 𝑊̇
̂ − )) = − 𝑠
∆ ( + + 𝑔𝑧 + (𝑈
𝜌 2 𝑚̇ 𝑚̇

Chapter 8: Balances on Non-Reactive Processes

When working with hypothetical paths:

• Know the boiling point and vaporization point of the substance
• Calculate an enthalpy value/internal energy for each change (temperature,
pressure, state of aggregation)
• Sum the enthalpies/internal energies for each step to get the overall change
for the designed path
• How to find enthalpies/internal energies?
For changes in pressure with constant temperature, internal energies will be
calculated.
𝑇2
̂ = ∫ 𝐶𝑣 𝑑𝑇
For ideal gases: ∆𝑈 𝑇1
𝑇2
̂ = ∫ 𝐶𝑣 𝑑𝑇 (approx.)
For solids and liquids: ∆𝑈 𝑇1

𝑇2 ̂2 𝜕𝑈
𝑉 ̂
̂ = ∫ 𝐶𝑣 𝑑𝑇 − ∫̂ ( ) 𝑑𝑉̂
For real gases: ∆𝑈 𝑇1 ̂ 𝑇
𝑉1 𝑑𝑉

For changes in temperature at constant pressure, enthalpies will be calculated.

̂ = ∫𝑇2 𝐶𝑝 𝑑𝑇
For ideal gases: ∆𝐻 𝑇 1

𝑇
̂ = ∫ 2 𝐶𝑝 𝑑𝑇 (approx.)
For solids and liquids: ∆𝐻 𝑇1

𝑇2 ̂2 𝜕𝐻
𝑉 ̂
̂ = ∫ 𝐶𝑝 𝑑𝑇 − ∫̂ ( ) 𝑑𝑉̂
For real gases: ∆𝐻 𝑇1 ̂ 𝑇
𝑉1 𝑑𝑉
Heat capacities (Cp) are calculated based on values in table B2. Enthalpy values of
specific gases can also be found in table B8.
Relationships between Cp and Cv:
For liquids and solids: 𝐶𝑝 = 𝐶𝑣
For ideal gases: 𝐶𝑝 = 𝐶𝑣 + 𝑅
No simple relation for real gases.
If not, they can be estimated using values for individual elements in table B10, and
calculated using Kopp’s rule.

𝐶𝑝,𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒 = ∑ 𝐶𝑝,𝑎𝑡𝑜𝑚𝑠

When a change of state occurs, the latent heat must be taken into account in the
enthalpy/internal energy calculations. These values can be found in table B1, BUT
only for the normal boiling point. This should be noted when designing
hypothetical paths.
To find the internal energies of fusion and vaporization, the following
approximations can be used:
̂𝑚 ≈ ∆𝐻
For the melting point: ∆𝑈 ̂𝑚
̂𝑣 ≈ ∆𝐻
For the boiling point: ∆𝑈 ̂𝑣 − 𝑅𝑇

If the standard heat of vaporization needs to be estimated, we have the following

approximations:
Trouton’s Rule (+/- 30% accuracy):
̂𝑣 ≈ 0.088𝑇𝑏 (𝐾)
For non-polar liquids: ∆𝐻
̂𝑣 ≈ 0.109𝑇𝑏 (𝐾)
For water and low molecular weight alcohols: ∆𝐻
Chen’s Equation (+/- 2% accuracy), Pc in atm, Tb and Tc in K:
0.0331𝑇𝑏
𝑇𝑏 [( ) − 0.0327 + 0.0297𝑙𝑜𝑔10 𝑃𝑐 ]
̂ 𝑇𝑐
∆𝐻𝑣 ≈
𝑇
1.07 − ( 𝑏 )
𝑇𝑐
Clapeyron Equation: See chapter 6
For all, the units of enthalpy is in kJ/mol
There are also correlations for calculating the latent heat of fusion, which are as
follows:
Heat of fusion empirical expressions:
• ∆𝐻
̂𝑚 ≈ 0.009288𝑇𝑚 (𝐾) for metallic elements
• ∆𝐻
̂𝑚 ≈ 0.0025𝑇𝑚 (𝐾) for inorganic compounds
• ∆𝐻
̂𝑚 ≈ 0.050𝑇𝑚 (𝐾) for organic compounds

Watson’s correlation:
𝑇𝑐 − 𝑇2 0.38
̂𝑣 (𝑇2 ) = ∆𝐻
∆𝐻 ̂𝑣 (𝑇1 ) ( )
𝑇𝑐 − 𝑇1
If there is heat absorbed or produced via mixing of compounds in solution, these
values can be found in table B11. Appropriate graphs will also be given (I hope).

Chapter 9: Balances on Reactive Processes

̂𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ ∆𝐻
Heat of reaction: ∆𝐻𝑟 (𝑇, 𝑃) = ∑ ∆𝐻 ̂𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

̂𝑟 (𝑇, 𝑃)
Adjusted for the extent of reaction: ∆𝐻 = 𝜉∆𝐻
̂𝑟 (𝑇, 𝑃) = ∆𝐻
At low to moderate pressures, we can assume that ∆𝐻 ̂𝑟 (𝑇)
Note that the standard heat of reaction takes place at 25 degrees Celsius and 1 atm.
Heats of reaction can be summed via Hess’s Law.
𝑛
̂𝑟 = ∑ 𝛼𝑖 Δ𝐻
Δ𝐻 ̂𝑟,𝑖
𝑖=2

Heat of reaction can also be calculated using standard heats of formation

̂°𝑟 =
Δ𝐻 ̂ °𝑓𝑗 −
∑ |𝜈𝑗 |Δ𝐻 ∑ ̂ °𝑓𝑖
|𝜈𝑖 |Δ𝐻
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

Note that elements at their REFERENCE STATES have enthalpies of formation of

0 (ex O2, H2, C, N2, etc. @ 25 degrees C)
Similarly, when dealing with combustible components, the heat of reaction can be
calculated using standard heats of combustion.

̂°𝑟 =
Δ𝐻 ̂ ° 𝑐𝑗 −
∑ |𝜈𝑗 |Δ𝐻 ∑ ̂ ° 𝑐𝑖
|𝜈𝑖 |Δ𝐻
𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

The energy balance equation for heat of reactions is as follows:

̂𝑟𝑗 °(𝑇, 𝑃) + ∑ 𝑛𝑖 𝐻
Δ𝐻 = ∑ 𝜉∆𝐻 ̂𝑖 − ∑ 𝑛𝑖 𝐻
̂𝑖
𝑜𝑢𝑡𝑙𝑒𝑡 𝑖𝑛𝑙𝑒𝑡

The standard enthalpy values should be calculated using a standard enthalpy table
for the inlet and outlet, including columns for moles and standard enthalpy, in
kJ/mol. To complete these calculations, reference states should be taken. In
general, we select references at 25 degrees C and 1 atm unless otherwise required
(example: to read certain charts, the reference point for water must be taken as its
triple point).
Thermochemistry of solutions:
̂ °𝑓,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = Δ𝐻
Heat of formation for a solution: Δ𝐻 ̂ °𝑓,𝑠𝑜𝑙𝑢𝑡𝑒 + Δ𝐻
̂ ° 𝑠 (𝑛)

The specific enthalpy of a solution is thus:

̂ °𝑓,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 + 𝑚 ∫𝑇2 𝐶𝑝,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑑𝑇, with m being the dissolved mass
̂𝑖 (𝑇) = Δ𝐻
𝐻 25°𝐶
corresponding to a mole of dissolved solute.
For fuels, there are two heating values listed, one high heating value and one low
heating value (table 9.6-1 in the textbook).
Formula: 𝐻𝐻𝑉 = 𝐿𝐻𝑉 + 𝑛∆𝐻𝑣 (𝐻2 𝑂, 25°𝐶)
Finally, we can equate the heat value (Q) to the heat of combustion via the energy
balance equation:
̂𝑐 ° + ∑ 𝑛𝑖 𝐻̂ (𝑇 ̂
𝑄̇ = ∆𝐻̇ = 𝜉̇ Δ𝐻 𝑖 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 ) − ∑ 𝑛𝑖 𝐻𝑖 (𝑇𝑓𝑒𝑒𝑑 ) = 0
𝑜𝑢𝑡𝑙𝑒𝑡 𝑖𝑛𝑙𝑒𝑡