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CHAPTER 4- ENERGY balance for non reactive system

Reference State ! A common practice is to arbitrarily designate a reference state for a substance at which U or H is declared to equal zero, and then tabulate U and/or H for the substance relative to the reference state. *Note: Refer Felder pp. 339 and 359 ! In Chapter 7 (Felder), U and H are state properties of a species; their values depend only on the state of the species primarily on its temperature and state of aggregation (solid, liquid or gas) and, to a lesser extent, on its pressure (and for mixtures of some species, on its mole fraction in the mixture). ! When a species passes from one state to another, both U and H for the process are independent of the path taken from the rst state to second one Hypothetical Process Path *Note: Refer Felder pp. 360

CHAPTER 4- ENERGY balance for non reactive system

CHANGES IN P AT CONSTANT T

CHANGES IN T AT CONSTANT P

PHASE CHANGE OPERATIONS

CHAPTER 4- ENERGY balance for non reactive system


CHANGES IN P AT CONSTANT T
! Internal energy (U) is nearly independent of pressure for solids and liquids at a xed temperature, as is specic volume (V) . *Note: Refer Felder pp. 365 366 ! If pressure of a solid and liquid changes at constant temperature U = 0 H = [U + (PV)] = [U + PV + V P] = [V P] ! Both U and H independent of pressure for ideal gases may assume U = 0 and H = 0 for a gas undergoing an isothermal pressure change unless gas temperature below 0 0C or well above 1 atm are involved.

CHAPTER 4- ENERGY balance for non reactive system

SENSIBLE HEAT AND HEAT CAPACITIES HEAT CAPACITY FORMULAS ESTIMATION OF HEAT CAPACITIES

CHAPTER 4- ENERGY balance for non reactive system


SENSIBLE HEAT AND HEAT CAPACITIES
! The term sensible heat signies that heat must be transferred to raise or lower the temperature of a substance or mixture of substances. *Note: Refer Felder pp. 366

! The quantity of heat required to produce a temperature change: Q = U (closed system) Q = H (open system)

! Heat capacity at constant volume Cv. At constant volume:


U = Cv (T )dT
T1 ^ T2

CHAPTER 4- ENERGY balance for non reactive system


SENSIBLE HEAT AND HEAT CAPACITIES
! Suppose both temperature and the volume of a substance change. To calculate U break the process into 2 steps ( a change in V at constant T followed by a changes in T and constant V):

A(T1 ,V1 ) A(T1 ,V2 ) A(T2 ,V2 ) U = U 1 + U 2


^ ^ ^

U 1

U 2

CHAPTER 4- ENERGY balance for non reactive system


SENSIBLE HEAT AND HEAT CAPACITIES
! For ideal gas and (to a good approximation) liquid and solids, U depends only on T. In step 1, T is constant, U1 = 0. Step 2 V is constant:
U = Cv (T )dT
T1 ^ T2

Ideal gas: Exact Solid or liquid: good approximation Non ideal gas: valid only if V is constant

CHAPTER 4- ENERGY balance for non reactive system


SENSIBLE HEAT AND HEAT CAPACITIES

Heat capacity at constant pressure Cp. At constant pressure:


H = C p (T ) dT
T1 ^ T2

! For rst step refer section 8.2 (Felder), as T is constant, H1 = 0 (for ideal gas), H1 = V P (for solid or liquid). Step 2 P is constant:
H = VP + C p (T )dT
T1 ^ ^ T2

Solid or liquid

Ideal gas: Exact H = C p (T )dT Non ideal gas: valid only if P T1 is constant
^ T2

CHAPTER 4- ENERGY balance for non reactive system


! Example Calculate the heat required to raise 200 kg nitrous oxide from 200C to 1500C in a constant volume vessel. The constant volume heat capacity in this temperature range is given by the equation:

C v kJ/kg 0 C = 0.855 + 9.42 10 4 T where T in 0 C


! Solution For vessel closed system. Q = U For constant volume: U = Cv (T )dT
T1 ^ T2

CHAPTER 4- ENERGY balance for non reactive system


! Solution
U =
^ ^ 150 20

(0.855 + 9.42 10 T ) dT
- 4 150

9.42 10 - 4 2 U = 0.855T + T = 0.855 (150 - 20 ) + 4.71 10 - 4 150 2 20 2 2 20 ^ kJ U = (111.15 + 10.4091) kg

)]

U = 121.5591

kJ 200 kg = 24 312 kJ kg

CHAPTER 4- ENERGY balance for non reactive system


HEAT CAPACITY FORMULAS
! Heat capacities are functions of temperature and frequently expressed in polynomial form (Cp = a + bT + cT2 + dT3). *Note: Refer Felder pp. 369

Liquid and Solids : C p = C v Ideal Gases : C p = C v + R R : Gas constant

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp369) Assuming ideal gas behavior, calculate the heat must be transferred in each of the following cases. 1. A stream of nitrogen owing at a rate of 100 mol/min is heated from 200C to 1000C 2. Nitrogen contained in 5 liter ask at an initial pressure of 3 bar is cooled from 900C to 300C Neglect the changes in kinetic energy

CHAPTER 4- ENERGY balance for non reactive system


! Solution Case 1 System: open system Q = H From Table B.2, Appendix B, the heat capacity of N2 at constant pressure of 1 atm:
Cp kJ/ mol0 C = 0.02900 + 0.2199 10 -5 T + 0.5723 10 -8 T 2 2.871 10 -12 T 3

[ (

)]

CHAPTER 4- ENERGY balance for non reactive system


!
H =
^ ^

Solution
100 20

(0.02900 + 0.2199 10

- 5

T + 0.5723 10 - 8 T 2 2.871 10 -12 T 3 dT


100

0.2199 10 - 5 2 0.5723 10 - 8 3 2.871 10 -12 4 H = 0.02900T + T + T T 2 3 4 20


^ ^ ^

H = 0.02900(100 - 20 ) + 0.1100 10 - 5 100 2 20 2 + 0.1908 10 - 8 100 3 20 3 0.7178 10 -12 100 4 20 4 H = 2.32 + 0.011 + 0.002 0.00007 H = 2.333 kJ/mol Finally, Q = H = 2.333
^

)]

kJ mol kJ 100 = 233.3 mol min min

Case 2 and Example 8.3 3 (pp 371): DIY

CHAPTER 4- ENERGY balance for non reactive system


ESTIMATION OF HEAT CAPACITIES
! Kopps rule simple empirical method for estimating the heat capacity of a solid or liquid near 200C. *Note: Refer Felder pp. 372

! Use Data in Table B.10 for Cp of atom compound


! Example: heat capacity of solid Ca(OH)2

(C ) (C )

p Ca (OH ) 2 p Ca (OH ) 2

= C pa

( )

Ca

+ 2 C pa

( )

+ 2 C pa

( )

= 26 + 2(17 ) + 2(9.6 ) J mol0 C

J J = 79 mol0 C mol0 C

True value is 89.5

CHAPTER 4- ENERGY balance for non reactive system


ESTIMATION OF HEAT CAPACITIES
! For heat capacities of certain mixture may use these rules:

Rules 1 : For a mixture of gases or liquids, calculate the total enthalpy change as the sum of the enthalpy changes for the pure mixture component

Rules 2 : For a highly dilute solutions of solids or gases in liquids, neglect the enthalpy change of solute.

CHAPTER 4- ENERGY balance for non reactive system


ESTIMATION OF HEAT CAPACITIES
! For heat capacities of certain mixture: (Cp)mix (T) ! For enthalpy calculation:
H =
^ T2

(C ) (T ) = y C (T )
p mix all mixture components i pi

T1

(C ) (T ) dT
p mix

( )

where C p mix = heat capacity of mixture yi = mass or mole fraction of i component

C pi = heat capacity of i component

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp373) Calculate the heat required to bring 150 mol/h of a stream containing 60% C2H6 and 40% C3H8 by volume from 00C to 4000C. Solution System: open system Q = H From Table B.2, Appendix B, the heat capacity of component:
Cpi C2H6 a b 0.04937 13.92 x 10-5 C3H8 0.06803 22.59 x 10-5 C2H6 0.02962 8.352 x 10-5 yi Cpi C3H8 0.0272 9.036 x 10-5 (Cp)mix kJ/mol.0C 0.05682 17.388 x 10-5

c -5.618 x 10-8 -13.11 x 10-8 -3.3708 x 10-8 -5.244 x 10-8 -8.6148 x 10-8 d 7.280 x 10-12 31.71 x 10-12 4.368 x 10-12 12.684 x 10-12 17.052 x 10-12

CHAPTER 4- ENERGY balance for non reactive system


!
^

Solution
400 0

H =
^

(0.05682 + 17.388 10

- 5

T 8.6148 10 - 8 T 2 + 17.052 10 -12 T 3 dT


400

17.388 10 - 5 2 8.6148 10 - 8 3 17.052 10 -12 4 H = 0.05682T + T T + T 2 3 4 0


- 8 17.388 10 - 5 8.6148 10 2 2 3 3 ( ) 0.05682 400 - 0 + 400 - 0 400 - 0 ^ 2 3 H = 17.052 10 -12 4 4 + 400 - 0 4 ^ kJ H = 22.728 + 13.9104 1.8378 + 0.1091 = 34.91 mol ^ kJ mol kJ H = 34.91 150 = 5237 mol h h

kJ mol

CHAPTER 4- ENERGY balance for non reactive system


PHASE CHANGE OPERATIONS
1) Latent Heats

! Latent heat the specic enthalpy change associated with the transition of a substance from one phase to another at constant temperature and pressure. *Note: Refer Felder pp. 378

! Latent heats for the two most commonly encountered phase changes are dened as follows: 1. Heat of fusion (or heating of melting) Hm (T,P) specic enthalpy dierence between the solid and liquid forms of a species at T and P 2. Heat of vaporization Hv (T,P) specic enthalpy dierence between the liquid and vapor forms of a species at T and P

CHAPTER 4- ENERGY balance for non reactive system


PHASE CHANGE OPERATIONS
2) Estimation and Correlation of Latent Heats

! Troutons rule a simple formula for estimating a standard heat of vaporization (Hv at normal boiling point); provide an estimate of Hv accurate to within 30%. *Note: Refer Felder pp. 381

H v (kJ/mol) 0.088Tb (K) nonpolar liquids 0.109Tb (K) water, low molecular weight alcohols Tb : normal boiling point of the liquid

CHAPTER 4- ENERGY balance for non reactive system


PHASE CHANGE OPERATIONS
2) Estimation and Correlation of Latent Heats

! Chens equation provides roughly 2% accuracy. *Note: Refer Felder pp. 381

H v (kJ/mol) =

Tb [0.0331 (Tb Tc ) 0.0327 + 0.0297 log10 Pc ] 1.07 (Tb Tc )

Tb : normal boiling point (K) Tc : critical temperature (K)

Pc : critical pressure (atm)

CHAPTER 4- ENERGY balance for non reactive system


PHASE CHANGE OPERATIONS
2) Estimation and Correlation of Latent Heats

! A formula for approximating a standard heat of fusion. *Note: Refer Felder pp. 381
H m (kJ/mol) 0.0092Tm (K) metallic elements 0.0025Tm (K) inorganic compounds 0.050Tm (K) organic compounds Tm : normal melting point of the solid
^

CHAPTER 4- ENERGY balance for non reactive system


PHASE CHANGE OPERATIONS
2) Estimation and Correlation of Latent Heats

! Watsons colleration a useful approximation for estimating Hv at T2 for known value at T1. *Note: Refer Felder pp. 382

Tc T2 H v (T2 ) = H v (T1 ) T T c 1 Tc : critical temperature


^ ^

0.38

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp379) 100 mole/h of liquid n-hexane (C6H14) at 250C and 7 bar is vaporized and heated to 3000C at constant pressure. Neglecting the eect of pressure on enthalpy, estimate the rate at which heat must be supplied. Given the boiling temperature of n-hexane at 7 bar is 1460C. Use data provided in Table B.1 to solve the problem.
HOW???

Analyze the information.

! P1 , T1 = 7 bar, 250C Liquid Phase ! P2 , T2 = 7 bar, 3000C Gas Phase ! Tb at 7 bar = 1460C

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp379) ! There is phase change operation, however the Hv at 1460C and 7 bar is not provided in the question. ! From Table B.1, Tb = 68.740C, Hv = 28.85 kJ/mol at P = 1 atm or 1.013 bar ! As stated in question, the eect of pressure on enthalpy is neglected

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp379) ! Path method
C6H14 (l) 250C, 7 bar 1 DH 1 = Cpdt (liq) C6H14 (l) 1460C, 7 bar 2 DH 2 = DH v C6H14 (v) 1460C, 7 bar 3 DH 3 = Cpdt (vap) C6H14 (v) 3000C, 7 bar 8 DH 8 = 0 (vap) C6H14 (v) 3000C, 1 atm

4 DH 4 = VDP (liq) C6H14 (l) 250C, 1 atm 5 DH 5 = Cpdt (liq) C6H14 (l) 68.740C, 1 atm 6 DH 6 = DH v C6H14 (v) 68.740C, 1 atm

7 DH 7 = Cpdt (vap)

! True process path 1 2 3 : Hv at 1460C and 7 bar is not provided ! Alternative process path 4 5 6 7 8

CHAPTER 4- ENERGY balance for non reactive system


! Example (Felder pp379) ! Calculate the enthalpy for each of stream number. ! Stream 4 ! Since the eect of pressure on enthalpy is neglected, H = 0

H 4 = VP H 4 = 0

CHAPTER 4- ENERGY balance for non reactive system


! Stream 5 ! Find Cp for liquid at Table B.2
H 5 =
68.74 25 3 3 (68.74 25 ) 216.3 10 dT = 216.3 10

H 5 = 9.461

kJ mol

Stream 6

H6 = Hv = 28.85

kJ mol

CHAPTER 4- ENERGY balance for non reactive system


! Stream 7 ! Find Cp for gas at Table B.2
H7 =
300 3 5 8 2 12 3 137.44 10 + 40.85 10 T 23.92 10 T + 57.66 10 T dT

68.74

H7 = 47.191

kJ mol

Stream 8

H8 = 0

CHAPTER 4- ENERGY balance for non reactive system


! Total enthalpy

H = H 4 + H 5 + H6 + H7 + H 8 H = 0 + 9.461 + 28.85 + 47.191 + 0 H = 85.502


!

kJ mol

For overall process

Q = nH = 100 Q = 2.375 kW

mol kJ 1 h 85.502 h mol 3600 s