Last Class 1

• Conclude discussion of specific enthalpy/internal energy calculations for changing T with a constant P

• Practice solving problems using energy balance methodology

 This Class 2

• Show how we can calculate specific enthalpy/internal energy for a system with changing P at constant T

• Show how we can calculate specific enthalpy/internal energy for a system with changing T at constant P
– Relationship to Heat Capacity (how to determine Heat Capacity)
 Estimation of Heat Capacities-Mixtures 3

• As we’ve seen we often need to know the properties of mixtures: heat capacity of a mixture approximated by:
𝐶𝑝 𝑇 = 𝑦𝑖 𝐶𝑝𝑖 (𝑇)
𝑚𝑖𝑥
𝑎𝑙𝑙
𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡𝑠
𝐶𝑝 𝑚𝑖𝑥 = Heat capacity of the mixture
𝑦𝑖 = mass or mole fraction i-th component
𝐶𝑝𝑖 = heat capacity of the pure i-th component
 Heat Capacities 4

• Once you have 𝐶𝑝 you can use it just as you would a normal 𝐶𝑝
𝑚𝑖𝑥
– Integrate between two temperatures and find ∆𝐻
– Subtract R and integrate to find ∆𝑈
 Heat Capacity of a Mixture 5

• Calculate the heat required to bring 150 mol/h of a stream containing 60% C2H6 and 40% C3H8 by volume from 0°C to
400°C. Determine a heat capacity for the mixture as a part of the problem solution.
 Estimation of Heat Capacities 6

• For solids and liquids there is an empirical method of estimating heat capacity if you have no tabulated heat capacity for
the compound (not listed in Table B.2)

• For Kopp’s rule, Cp is equal to the sum of contributions (Table B.10) for each element in the compound
– This Cp can then be used in the integral we defined
– Best used at or near 20°C
 Example 7

• A liquid mixture of 30 wt% acetone and 70 wt% 2-methyl-1-pentanol (C6H14O) is cooled from 45°C to 20°C. Calculate the
associated specific enthalpy change in J/g, using Kopp’s rule to estimate any heat capacity for which a tabulated value
cannot be found.
 Calculating Internal Energy and Enthalpy Changes 8

• Changes in P at constant T and state of aggregation (phases) (Section 8.2)

• Changes in T at constant P and state of aggregation (Section 8.3)
• Phase changes at constant T and P (e.g. melting evaporating, solidifying) (Section 8.4)
• Mixing of two liquids or dissolving of a gas or a solid in a liquid at constant T and P (Section 8.5)
• Chemical reaction at constant T and P (Chap. 9)
 General Procedure for Energy Balance Calculations 9

• We now have the information necessary to perform energy balances on any processes that do not involve phase changes
(excluding water), changes in enthalpy due to mixing/dissolution, and chemical reactions

• We previously introduced the general procedure for performing energy balance calculations
– This procedure is valid even if there are phase changes, chemical reactions, etc.
 10
1. Draw a flowchart
2. Perform all required material balance calculations
3. Write the appropriate form of the energy balance and simplify
4. Choose a reference state for each species involved
5. Construct a table for initial and final amounts (or flow rates) of each species and specific internal energies (or enthalpies) relative
to the chosen reference state
6. Calculate all required values of 𝑈 and 𝐻 and fill in the table
7. Calculate ΔU (or ΔH)
8. Calculate any work, kinetic energy, or potential energy terms that you have not dropped from the energy balance
9. Solve the energy balance for the unknown variable
 Reference States 11

• Its important to remember that it is not possible to determine exact values of 𝑈 and 𝐻 but it is possible to determine
changes/differences (Δ) in 𝑈 and 𝐻 (what we care about anyway)

• The procedure now has you choose a reference state

– If tabulated values of 𝑈 (or 𝐻) are given, use the reference state defined in the table
– Otherwise choose one of the inlet or outlet states as the reference state for the species
– At the reference state: energies set to zero
 Example 12

Propane gas enters a continuous adiabatic heat exchanger at 40°C and 250 kPa and exits at 240°C. Superheated steam at
300°C and 5.0 bar enters the exchanger flowing countercurrently to the propane and exits as a saturated liquid at the same
pressure.
a) Taking as a basis 100 mol of propane fed to the exchanger, draw and label a process flowchart.
b) Calculate values of the labeled specific enthalpies in an enthalpy table
 Example 13

Propane gas enters a continuous adiabatic heat exchanger at 40°C and 250 kPa and exits at 240°C. Superheated steam at
300°C and 5.0 bar enters the exchanger flowing countercurrently to the propane and exits as a saturated liquid at the same
pressure.
c) Use an energy balance to calculate the required mass feed rate of the steam. Then calculate the volumetric feed ratio
of the two streams. Assume ideal gas for the propane but not the steam
 Example 14

Propane gas enters a continuous adiabatic heat exchanger at 40°C and 250 kPa and exits at 240°C. Superheated steam at
300°C and 5.0 bar enters the exchanger flowing countercurrently to the propane and exits as a saturated liquid at the same
pressure.
d) Calculate the heat transferred from the water to the propane (kJ/m3 propane fed). (Hint: Do an energy balance on
either the water or the propane rather than on the entire heat exchanger.)
 15
1. Draw a flowchart
2. Perform all required material balance calculations
3. Write the appropriate form of the energy balance and simplify
4. Choose a reference state for each species involved
5. Construct a table for initial and final amounts (or flow rates) of each species and specific internal energies (or enthalpies) relative
to the chosen reference state
6. Calculate all required values of 𝑈 and 𝐻 and fill in the table
7. Calculate ΔU (or ΔH)
8. Calculate any work, kinetic energy, or potential energy terms that you have not dropped from the energy balance
9. Solve the energy balance for the unknown variable
 Energy Balance on a Gas Preheater 16

• A stream containing 10% CH4 and 90% air by volume is to be heated from 20°C to 300°C. Calculate the required rate of
heat input in kilowatts if the flow rate of the gas is 2.00 x 103 liters (STP)/min. (Example 8.3-5)