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ChE 2800 - Spring 2002

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Basic Concepts

Definitions:

• System: Any specified mass of material or piece(s) of equipment we wish to devote our

attention to.

– closed: No transfer of mass across the system boundaries.

– open: Transfer of mass across the system boundaries is permitted.

• Surroundings: Anything that is not part of the system.

• Properites: A characteristic of the material that can be calculated or measured.

– extensive: A property that is the sum of the values of each of the subsystems

comprising the whole system. A property dependent on system size.

∗ Example: mass or volume.

– intensive: A property whose value is not additive, and does not vary with system

size.

∗ Example: temperature, pressure, density

– specific: An intensive property that is obtained by dividing an extensive property

by the total amount of process material.

∗ Example: A liquid where V = 200 cm3 and the mass = 200 g, then the specific

volume Vˆ = 1 cm3 /g.

• State: A set of properites of the material at a point in time. The state of a system

depends only on the system’s intensive properties.

1.1

Work

**The term “Work” is used widely in casual conversation, but in this context we refer to a specific
**

definition. Work is a form of energy that represents a transfer of energy between the system

1 m3 to 0. For this reason. • State function: A function that is only dependent upon the initial and final states of the system. For a mechanical force: W = Z state 2 state 1 F · dl (1) where F is an external force in the direction of l acting on the system. Calculate the work done by the gas on the piston if: • Path 1: expansion occurs at constant pressure (p = 500 kPa) • Path 2: expansion occurs at constant temperature (T = 300 K) W = Z V2 F V1 Z V2 p dV (2) p dV = p (V2 − V1 ) (3) A · A dl = V1 Path 1 W = Z V2 V1 5 = 5. enthalpy.Energy Balances ChE 2800 .1 Illustration of work as a path function An ideal gas at 300 K and 500 kPa is enclosed in a cylinder capped by a frictionless piston. heat. The gas slowly expands from 0. – Example: work.00 × 10 kPa (0.2 m3 .2 m3 − 0. we say that work is a path function.Spring 2002 2/13 and surroundings. – Example: internal energy. or a system force acting on the surroundings. • Path function: A function who’s final value is dependent on the path taken to get from the initial to final state.1. 1. The amount of work done by a system on its surroundings (or by the surroundings on the systems) is dependent upon the inital and final states of the system and the path taken to get from state 1 to state 2.1 m3 ) = 50kJ .

795 m/s v = V˙ /A = π(0.02)2 m2 (8) .1 Example: Calculation of Kinetic Energy Water is pumped from a storage tank into a 4.3 Kinetic Energy • Kinetic energy (KE): The energy a system possesses because of a velocity difference between it and it’s surroundings at rest.3. is a path function.1) = 34. Heat.0 mol RT (300K)(8.Energy Balances ChE 2800 .2 Z V2 V1 p dV = Z V2 nRT V nRT ln(V2 /V1 ) V1 dV (4) PV (5.57kJ (6) Heat • Heat (Q): The part of the total energy flow across a system boundary that is caused by a temperature difference between the system and its surroundings.001 m3 /s.0 cm ID tube at a rate of 0. What is the kinetic energy of the water? • Step 1.001m3 /s = 0. Path 2 W = = 1. 1 KE = mv 2 2 (7) where m is the mass of the object and v is the object’s velocity relative to the reference state.0 × 105 Pa)(0.314 Pa m3 /mol K)(300K) ln(0. like work. 1.314 Pa m3 /mol K) (5) W = (20.1m3 ) n= = = 20.2/0. determine the linear velocity of the water 0.Spring 2002 3/13 Remember 1 J = 1 N·m.0mol)(8. 1.

0 J/kg (12) .Spring 2002 4/13 • Step 2. What is the increase in the potential energy of the water per kg of water moved (the increase in the specific PE of the water)? P E = mgh = (9.795 m/s)2 = 0.807 m/s2 ).4 Potential Energy • Potential Energy (PE): The energy a system possesses because of forces exerted on its mass by gravitational or electromagnetic fields with respect to a reference surface. find the mass flow rate of mater ρ = m/V . m is the mass of the object and g is the acceleration due to gravity (9.0 kg/s (9) • Step 3. ρV˙ = m.1 Example: Calculation of Potential Energy Water is pumped from one reservoir to a second reservoir 10 m above the water level of the first.80 m/s2 )(10m) = 98. 1.0 kg/s)(0. ˙ (1000 kg/m3 )(0. P E = mgh (11) where h is the distance from the reference surface. calculate the kinetic energy 1 2 1 ˙ = (1.4.316 J/s KE = mv 2 2 (10) • check units – 1 N = kg · m/s2 – 1J=N·m – Therefore: (kg · m/s2 )(m/s) = N· m/s = J/s 1.001 m3 /s) = 1.Energy Balances ChE 2800 .

but is instead calculated from other variables that can be measured. such as pressure. one phase system that specifying two intensive variables will definite U . p) (18) • Taking the derivative yields: Ã ˆ = dH ˆ ∂H ∂T ! Ã ˆ ∂H dT + ∂p p ! dp T (19) .5 ChE 2800 . is a state function and is defined: H = U + pV (17) • for a one component. atomic and subatomic energies contained within a fluid. From the Gibbs phase rule we know for a one componet. Uˆ2 − Uˆ1 = 1.Energy Balances 1. Cannot be measured. Vˆ ) (13) • Taking the derivative yields Ã dUˆ = • Note: ∂ Uˆ ∂T Ã Cv = Ã ! Vˆ ∂ Uˆ ∂T ∂ Uˆ dT + ∂ Vˆ ! Ã . changes in Uˆ can be calculated by integration of equation 14.Spring 2002 5/13 Internal Energy • Internal Energy (U ): A macroscopic measure of the molecular. V ∂ Uˆ ∂ Vˆ ! dVˆ (14) T ! ≈0 (15) T • Therefore. temperature and volume. one phase system: H = f (T. • Uˆ is commonly defined in terms of T and Vˆ Uˆ = f (T.6 Z T2 T1 Cv dT (16) Enthalpy • Enthalpy (H): Enthalpy. • U is a state function. like U .

. • Therefore.Spring 2002 • Note: Ã Cp = ˆ ∂H ∂T ! Ã . changes in H ˆ2 − H ˆ1 = H Z T2 T1 Cp dT (21) Again. p ˆ ∂H ∂p 6/13 ! ≈0 (20) T ˆ can be calculated by integration of equation 19. Only differences in U or H relative to a reference state may be calculated. we note that the absolute values of both U and H cannot be calculated directly.Energy Balances ChE 2800 .

Uˆ2 − Uˆ1 = Z T2 T1 Cv dT • This equation is valid under the following conditions: – Exact for ideal gases – A good approximation for liquids and solids – Only valid for a non-ideal gas if V = constant. it is possible to determine the change in internal energy (∆U . • Knowing the sensible heat and the latent heat.Spring 2002 7/13 Heat Capacities Definitions: • Sensible heat: The heat that must be transfered to raise or lower the temperature of a substance(s). ˆ v ): The specific enthalpy difference between the liquid – Heat of vaporization (∆H and vapor forms of a substance at a given T and P . • The determination of ∆U for a system that does not undergo a phase transition is straightforward. liquidvapor) of a substance at constant T and P . (24) . ˆ v and ∆H ˆ m are strong functions of T . or the enthalpy (∆H.g. Q = ∆U (closed system) (22) Q˙ = ∆H˙ (open system) (23) • Latent heat: The specific enthalpy change associated with a phase transition (e. but only weak functions of – NOTE: Both ∆H P.Energy Balances 2 ChE 2800 . ˆ m ): The specific enthalpy difference between the solid and – Heat of fusion (∆H liquid forms of a substance at a given T and P . closed system). open system).

Energy Balances ChE 2800 . the Vˆ ∆P term in the above equation is usually negligible compared to the second term.90 × 10−8 T 2 + 80. 1 mol of liquid cyclohexane is stored in a covered beaker at 1 atm and 20 ◦ C. Cp ≈ Cv for liquid cyclohexane.1 Example of a ∆U Calculation from Cv .Spring 2002 8/13 • We can write a similar expression for ∆H: ˆ2 − H ˆ1 = H Z T2 T1 Cp dT (25) • This equation is valid under the following conditions: – Exact for ideal gases – Only valid for a non-ideal gas if P = constant.62 × 10−5 T − 31. taken from Table B. • For a closed system. • Cp and Cv are related to each other in the following way: – For liquids and solids Cp ≈ Cv – Ideal gases Cp = Cv + R 2.140 × 10−3 + 49. Calculate the energy input required to heat the cyclohexane to 60 ◦ C. – For liquids or solids: ˆ2 − H ˆ 1 = Vˆ ∆P + H Z T2 T1 Cp dT (26) However.63 × 10−12 T 3 (28) .2 [kJ/(mol ◦ C)]is: Cv = 94. the energy balance becomes: Q = n∆Uˆ (27) • ∆U may be calculated from integration of 14.

so it doesn’t matter what path we take to get from • Fortunately H point A to point B. 3 atm) (31) ˆ for each state.582 kJ/mol ∆U (29) (30) • Since Q = n∆Uˆ . 25◦ C. 2.140 × 10−3 (T2 − T1 ) 49.Spring 2002 9/13 • Integration of 28 yields: ∆Uˆ = 94. a more complex procedure to calculate the amount of heat required.0 mol)(4. liquid to vapor. ˆ ˆ ∆H 300◦ C. • ∆H The change in the enthalpy for the process is simply the sum of the enthalpy changes for each leg of the hypothetical process path.62 × 10−5 2 (T2 − T12 ) + 2 31. ˆ can be evaluated by constructing a convenient alternate path.90 × 10−8 3 − (T2 − T13 ) 3 80.582 kJ/mol) = 4.63 × 10−12 4 + (T2 − T14 ) 4 ˆ = 4.582 kJ If the fluid undergoes a change of phase (solid to liquid. 1 atm) − H(solid.2 Hypothetical Process Paths Suppose we wish to calculate the heat required to turn solid phenol at 25◦ C and 1 atm to vapor at 300 ◦ C at 3 atm.we don’t know H ˆ is a state function. etc). • Problem .Energy Balances ChE 2800 . ˆ = ∆H ˆ 1 + ∆H ˆ 2 + ∆H ˆ 3 + ∆H ˆ 4 + ∆H ˆ 5 + ∆H ˆ6 ∆H (32) . ˆ = H(vapor. Q =(1.

Energy Balances ChE 2800 . Step 1.4.85 kJ/mol at 69 ◦ C.817 ) T + 224. Since Tboil 6= Tn−boil . solid 42. 1 atm. The change in enthalpy for this process is given by: ˆ = ∆H ˆ 1 + ∆H ˆ 2 + ∆H ˆ3 ∆H (34) ˆ values for each leg of our hypothetical process.3 ˆ Calculation Example of ∆H 100 mol of liquid hexane at 25 ◦ C and 7 bar is vaporized and heated to 300 ◦ C at constant pressure. Red line denotes actual path. 2. liquid dH4 181. ∆H • Find Tboil (7 bar). vapor. collect data ˆ v = 28.Spring 2002 dH6 300 C.867 (33) • Solve for T .4 C. vapor. Tboil = 144 ◦ C. solid Figure 1: Hypothetical process path for the vaporization of Phenol. determine the ∆H ˆ 1 = Vˆ ∆P + ∆H Z 69 25 216. log p∗ = (6. 1 atm 10/13 300 C. we need to construct a hypothetical process path to get from the initial to final states.5 C. vapor dH3 dH2 42.1.5 C. Step 2. black line denotes the hypothetical process path. 3 atm dH5 181.3 × 10−3 dT (35) . • From table B.88555 − 1175. liquid dH1 25 C.

517 × 10−3 m3 /kg.85 × 10−5 T +23.0785 kJ/h + 951.7 + 2885 + 4714.01325 − 7. vap dH3 dH2 69 C.617) × (1. Vˆ = 1/ρ = 1.617 × 10−3 kg ∆H1 = (8.0) ×(1.44 × 10−3 + 40.7 kJ/h (37) ∆H2 = (100)(28. vap 69 C. liq Figure 2: Hypothetical process path for the vaporization of Hexane.8 = 8551 kJ/h (41) .2163(69 − 25)) ∆H3 = (36) ∆H1 = −0. 7 bar. • ρ = 0.517 × 10−3 )(1.01325 × 105 ) +100(0.17 g/mol = 8617 g or 8.92 × 10−8 T 2 + 57.0785 + 951.66 × 10−12 T 3 dT ∆H3 = 4714.85 kJ/h (39) (40) Sum values of ∆H determined above: ∆H = −0. 1 bar.85) = 2885 kJ/h (38) Z 300 69 137.659 g/cm3 .Energy Balances ChE 2800 . liq dH1 25 C. • 100 mol*86. 1 bar. 7 bar.Spring 2002 11/13 300 C.

0297 log Pc ] 1. the general balance equation beomes: accumulation = input − output (46) or final system energy − inital system energy = net energy transfered to system (47) .109Tb (water.07 − (Tb /Tc ) (43) ˆ v = [kJ/mol].0331(Tb /Tc ) − 0.4 ChE 2800 .050Tm (organic compounds) (45) Energy Balances on Closed Systems Remember. low MW alcohols) (42) ˆ v = [kJ/mol] and Tb =[K].088Tb (non − polar fluids) ≈ 0.0025Tm (inorganic compounds) ≈ 3 0. Tb .0092Tm (metallic elements) ≈ 0.Spring 2002 12/13 Estimation of Latent Heats • Trouton’s Rule: ˆv ≈ ∆H 0. Watson’s Correlation can be used to predict • If ∆H ˆ v at a different temperature ∆H ˆ v (T2 ) = ∆H ˆ v (T1 ) ∆H µ Tc − T2 Tc − T1 ¶0. In this case. – where ∆H ˆ v is known for one temperature. one should use Chen’s equation ˆv = ∆H Tb [0.0327 + 0. Tc =[K] and Pc = [atm]. – where ∆H • For greater accuracy.38) (44) ˆ m ) when experi• The following relationships can be used to predict heats ofr fusion (∆H mental data is not availible ˆm ≈ ∆H 0.Energy Balances 2. a closed system is one where there is no transfer of material across the system boundary.

Q = 0. liquid) of the system materials. – If the system is not rising or falling. or the system is perfectly insultated. ∆KE = 0. 4 Energy Balances for Open Systems In an open system. – If there are no moving parts. temperature.Energy Balances ChE 2800 . and phase (gas. electrical currents or radiation at the system boundary. ∆P E = 0. This kind of process is refered to as adiabatic. ∆U ≈ 0 – If the system is not accelerating or decelerating (v = 0). phase changes or chemical reactions. solid. The general balance equation in this case becomes simply: input = output and ∆H + ∆KE + ∆P E = Q + W (52) . – For a closed system with no ∆T . mass is allowed to cross the system boundaries. – If the system and its surroundings are at the same temperature.Spring 2002 13/13 • initial system energy Ui + KEi + P Ei (48) Uf + KEf + P Ef (49) Q+W (50) • final system energy • energy transfered • Combining the above equations we can write the energy balance for a closed system ∆U + ∆KE + ∆P E = Q + W (51) • NOTES: – U depends almost entirely on chemical composition. W = 0.

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